Sample records for ultra-high-performance liquid chromatography-tandem

  1. Ultra-high-pressure liquid chromatography-tandem mass spectrometry method for the determination of alkylphenols in soil.

    PubMed

    Wang, Jing; Pan, Hefang; Liu, Zhengzheng; Ge, Fei

    2009-03-20

    A novel method has been developed for the determination of alkylphenols in soil by ultra-high-pressure liquid chromatography employing small particle sizes, combined with tandem mass spectrometry. Soil samples were extracted with pressurized liquid extraction (PLE) and then cleaned with solid-phase extraction (SPE). The extracts were separated on C18 column (1.7 microm, 50 mm x 2.1mm) with a gradient elution and a mobile phase consisting of water and acetonitrile, and then detected by an electrospray ionization tandem mass spectrometry in negative ion mode with multiple reaction monitoring (MRM). Compared with traditional liquid chromatography, it took ultra-high-pressure liquid chromatography much less time to analyze alkylphenols. Additionally, the ultra-high-pressure liquid chromatography/tandem mass spectrometry method produces satisfactory reliability, sensitivity, and accuracy. The average recoveries of the three target analytes were 74.0-103.4%, with the RSD<15%. The calibration curves for alkylphenols were linear within the range of 0.01-0.4 microg/ml, with the correlation coefficients greater than 0.99. When 10 g soil sample was used for analysis, the limits of quantification (LOQs) of the three alkylphenols were all 1.0 microg/kg.

  2. Comparison of ultra high performance supercritical fluid chromatography, ultra high performance liquid chromatography, and gas chromatography for the separation of synthetic cathinones.

    PubMed

    Carnes, Stephanie; O'Brien, Stacey; Szewczak, Angelica; Tremeau-Cayel, Lauriane; Rowe, Walter F; McCord, Bruce; Lurie, Ira S

    2017-09-01

    A comparison of ultra high performance supercritical fluid chromatography, ultra high performance liquid chromatography, and gas chromatography for the separation of synthetic cathinones has been conducted. Nine different mixtures of bath salts were analyzed in this study. The three different chromatographic techniques were examined using a general set of controlled synthetic cathinones as well as a variety of other synthetic cathinones that exist as positional isomers. Overall 35 different synthetic cathinones were analyzed. A variety of column types and chromatographic modes were examined for developing each separation. For the ultra high performance supercritical fluid chromatography separations, analyses were performed using a series of Torus and Trefoil columns with either ammonium formate or ammonium hydroxide as additives, and methanol, ethanol or isopropanol organic solvents as modifiers. Ultra high performance liquid chromatographic separations were performed in both reversed phase and hydrophilic interaction chromatographic modes using SPP C18 and SPP HILIC columns. Gas chromatography separations were performed using an Elite-5MS capillary column. The orthogonality of ultra high performance supercritical fluid chromatography, ultra high performance liquid chromatography, and gas chromatography was examined using principal component analysis. For the best overall separation of synthetic cathinones, the use of ultra high performance supercritical fluid chromatography in combination with gas chromatography is recommended. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. [Qualitative and quantitative analysis of amygdalin and its metabolite prunasin in plasma by ultra-high performance liquid chromatography-tandem quadrupole time of flight mass spectrometry and ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometry].

    PubMed

    Gao, Meng; Wang, Yuesheng; Wei, Huizhen; Ouyang, Hui; He, Mingzhen; Zeng, Lianqing; Shen, Fengyun; Guo, Qiang; Rao, Yi

    2014-06-01

    A method was developed for the determination of amygdalin and its metabolite prunasin in rat plasma after intragastric administration of Maxing shigan decoction. The analytes were identified by ultra-high performance liquid chromatography-tandem quadrupole time of flight mass spectrometry and quantitatively determined by ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometry. After purified by liquid-liquid extraction, the qualitative analysis of amygdalin and prunasin in the plasma sample was performed on a Shim-pack XR-ODS III HPLC column (75 mm x 2.0 mm, 1.6 microm), using acetonitrile-0.1% (v/v) formic acid aqueous solution. The detection was performed on a Triple TOF 5600 quadrupole time of flight mass spectrometer. The quantitative analysis of amygdalin and prunasin in the plasma sample was performed by separation on an Agilent C18 HPLC column (50 mm x 2.1 mm, 1.7 microm), using acetonitrile-0.1% (v/v) formic acid aqueous solution. The detection was performed on an AB Q-TRAP 4500 triple quadrupole mass spectrometer utilizing electrospray ionization (ESI) interface operated in negative ion mode and multiple-reaction monitoring (MRM) mode. The qualitative analysis results showed that amygdalin and its metabolite prunasin were detected in the plasma sample. The quantitative analysis results showed that the linear range of amygdalin was 1.05-4 200 ng/mL with the correlation coefficient of 0.999 0 and the linear range of prunasin was 1.25-2 490 ng/mL with the correlation coefficient of 0.997 0. The method had a good precision with the relative standard deviations (RSDs) lower than 9.20% and the overall recoveries varied from 82.33% to 95.25%. The limits of detection (LODs) of amygdalin and prunasin were 0.50 ng/mL. With good reproducibility, the method is simple, fast and effective for the qualitative and quantitative analysis of the amygdalin and prunasin in plasma sample of rats which were administered by Maxing shigan decoction.

  4. Simultaneous determination of phenolic compounds in Equisetum palustre L. by ultra high performance liquid chromatography with tandem mass spectrometry combined with matrix solid-phase dispersion extraction.

    PubMed

    Wei, Zuofu; Pan, Youzhi; Li, Lu; Huang, Yuyang; Qi, Xiaolin; Luo, Meng; Zu, Yuangang; Fu, Yujie

    2014-11-01

    A method based on matrix solid-phase dispersion extraction followed by ultra high performance liquid chromatography with tandem mass spectrometry is presented for the extraction and determination of phenolic compounds in Equisetum palustre. This method combines the high efficiency of matrix solid-phase dispersion extraction and the rapidity, sensitivity, and accuracy of ultra high performance liquid chromatography with tandem mass spectrometry. The influential parameters of the matrix solid-phase dispersion extraction were investigated and optimized. The optimized conditions were as follows: silica gel was selected as dispersing sorbent, the ratio of silica gel to sample was selected to be 2:1 (400/200 mg), and 8 mL of 80% methanol was used as elution solvent. Furthermore, a fast and sensitive ultra high performance liquid chromatography with tandem mass spectrometry method was developed for the determination of nine phenolic compounds in E. palustre. This method was carried out within <6 min, and exhibited satisfactory linearity, precision, and recovery. Compared with ultrasound-assisted extraction, the proposed matrix solid-phase dispersion procedure possessed higher extraction efficiency, and was more convenient and time saving with reduced requirements on sample and solvent amounts. All these results suggest that the developed method represents an excellent alternative for the extraction and determination of active components in plant matrices. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Simultaneous determination of four alkaloids in Lindera aggregata by ultra-high-pressure liquid chromatography-tandem mass spectrometry.

    PubMed

    Han, Zheng; Zheng, Yunliang; Chen, Na; Luan, Lianjun; Zhou, Changxin; Gan, Lishe; Wu, Yongjiang

    2008-11-28

    A new separation and quantification method using liquid chromatography under ultra-high-pressure in combination with tandem mass spectrometry (MS/MS) was developed for simultaneous determination of four alkaloids in Lindera aggregata. The analysis was performed on an Acquity UPLC BEH C(18) column (50mmx2.1mm, 1.7microm particle size; Waters, Milford, MA, USA) utilizing a gradient elution profile and a mobile phase consisting of (A) water containing 10mM ammonium acetate adjusted to pH 3 with acetic acid and (B) acetonitrile. An electrospray ionization (ESI)-tandem interface in the positive mode was employed prior to mass spectrometric detection. The calibration curve was linear over the range of 17.1-856ng for boldine, 42.4-2652ng for norboldine, 6.1-304ng for reticuline and 0.5-50ng for linderegatine, respectively. The average recoveries ranged from 99.2 to 101.4% with RSDs< or =2.7%. Then, four L. aggregata samples from different batches were analyzed using the established method. The results indicated that ultra-high-pressure liquid chromatography-tandem mass spectrometry provided improved chromatographic parameters resulting in significantly increased sample throughput including lower solvent consumption and lower limits of quantitation (LOQs) for most of target analytes compared to previous method employing conventional high-performance liquid chromatography (HPLC) separation. So, the established method was validated, sensitive and reliable for the determination of four alkaloids in L. aggregata.

  6. High-throughput quantification for a drug mixture in rat plasma-a comparison of Ultra Performance liquid chromatography/tandem mass spectrometry with high-performance liquid chromatography/tandem mass spectrometry.

    PubMed

    Yu, Kate; Little, David; Plumb, Rob; Smith, Brian

    2006-01-01

    A quantitative Ultra Performance liquid chromatography/tandem mass spectrometry (UPL/MS/MS) protocol was developed for a five-compound mixture in rat plasma. A similar high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) quantification protocol was developed for comparison purposes. Among the five test compounds, three preferred positive electrospray ionization (ESI) and two preferred negative ESI. As a result, both UPLC/MS/MS and HPLC/MS/MS analyses were performed by having the mass spectrometer collecting ESI multiple reaction monitoring (MRM) data in both positive and negative ion modes during a single injection. Peak widths for most standards were 4.8 s for the HPLC analysis and 2.4 s for the UPLC analysis. There were 17 to 20 data points obtained for each of the LC peaks. Compared with the HPLC/MS/MS method, the UPLC/MS/MS method offered 3-fold decrease in retention time, up to 10-fold increase in detected peak height, with 2-fold decrease in peak width. Limits of quantification (LOQs) for both HPLC and UPLC methods were evaluated. For UPLC/MS/MS analysis, a linear range up to four orders of magnitude was obtained with r2 values ranging from 0.991 to 0.998. The LOQs for the five analytes ranged from 0.08 to 9.85 ng/mL. Three levels of quality control (QC) samples were analyzed. For the UPLC/MS/MS protocol, the percent relative standard deviation (RSD%) for low QC (2 ng/mL) ranged from 3.42 to 8.67% (N = 18). The carryover of the UPLC/MS/MS protocol was negligible and the robustness of the UPLC/MS/MS system was evaluated with up to 963 QC injections. Copyright 2006 John Wiley & Sons, Ltd.

  7. Chemical fingerprint of Ganmaoling granule by double-wavelength ultra high performance liquid chromatography and ultra high performance liquid chromatography with quadrupole time-of-flight mass spectrometry.

    PubMed

    Lou, Qiong; Ye, Xiaolan; Zhou, Yingyi; Li, Hua; Song, Fenyun

    2015-06-01

    A method incorporating double-wavelength ultra high performance liquid chromatography with quadrupole time-of-flight mass spectrometry was developed for the investigation of the chemical fingerprint of Ganmaoling granule. The chromatographic separations were performed on an ACQUITY UPLC HSS C18 column (2.1 × 50 mm, 1.8 μm) at 30°C using gradient elution with water/formic acid (1%) and acetonitrile at a flow rate of 0.4 mL/min. A total of 11 chemical constituents of Ganmaoling granule were identified from their molecular weight, UV spectra, tandem mass spectrometry data, and retention behavior by comparing the results with those of the reference standards or literature. And 25 peaks were selected as the common peaks for fingerprint analysis to evaluate the similarities among 25 batches of Ganmaoling granule. The results of principal component analysis and orthogonal projection to latent structures discriminant analysis showed that the important chemical markers that could distinguish the different batches were revealed as 4,5-di-O-caffeoylquinic acid, 3,5-di-O-caffeoylquinic acid, and 4-O-caffeoylquinic acid. This is the first report of the ultra high performance liquid chromatography chemical fingerprint and component identification of Ganmaoling granule, which could lay a foundation for further studies of Ganmaoling granule. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Simultaneous determination of nitroimidazoles, benzimidazoles, and chloramphenicol components in bovine milk by ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Wang, Yuanyuan; Li, Xiaowei; Zhang, Zhiwen; Ding, Shuangyang; Jiang, Haiyang; Li, Jiancheng; Shen, Jianzhong; Xia, Xi

    2016-02-01

    A sensitive, confirmatory ultra-high performance liquid chromatography-tandem mass spectrometric method was developed and validated to detect 23 veterinary drugs and metabolites (nitroimidazoles, benzimidazoles, and chloramphenicol components) in bovine milk. Compounds of interest were sequentially extracted from milk with acetonitrile and basified acetonitrile using sodium chloride to induce liquid-liquid partition. The extract was purified on a mixed mode solid-phase extraction cartridge. Using rapid polarity switching in electrospray ionization, a single injection was capable of detecting both positively and negatively charged analytes in a 9 min chromatography run time. Recoveries based on matrix-matched calibrations and isotope labeled internal standards for milk ranged from 51.7% to 101.8%. The detection limits and quantitation limits of the analytical method were found to be within the range of 2-20 ng/kg and 5-50 ng/kg, respectively. The recommended method is simple, specific, and reliable for the routine monitoring of nitroimidazoles, benzimidazoles, and chloramphenicol components in bovine milk samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Salting-out assisted liquid-liquid extraction coupled to ultra-high performance liquid chromatography-tandem mass spectrometry for the determination of tetracycline residues in infant foods.

    PubMed

    Moreno-González, David; García-Campaña, Ana M

    2017-04-15

    The use of salting-out assisted liquid-liquid extraction (SALLE) combined with ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) has been evaluated for the determination of tetracyclines in infant foods based on meat and vegetables or in milk. To obtain satisfactory extraction efficiencies for the studied analytes, several parameters affecting the SALLE procedure were optimized. Analytical performances of the method were satisfactory, obtaining limits of quantification lower than 0.48μgkg -1 in all cases. The precision, expressed as relative standard deviation (%, RSD) was below 11.3%. The extraction efficiency for fortified samples ranged from 89.2 to 96.8%, with RSDs lower than 7.3%. Matrix effect was evaluated for all samples studied, being lower than |21|% in all cases. In relation to the low solvent consumption, the proposed methodology could be considered rapid, cheap and environmentally friendly. Its applicability has been successfully tested in a wide range of infant foods. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Ultra-high performance liquid chromatography tandem high-resolution mass spectrometry study of tricyclazole photodegradation products in water.

    PubMed

    Gosetti, Fabio; Chiuminatto, Ugo; Mazzucco, Eleonora; Mastroianni, Rita; Bolfi, Bianca; Marengo, Emilio

    2015-06-01

    This paper reports the study of the photodegradation reactions that tricyclazole can naturally undergo, under the action of sunlight, in aqueous solutions of standard tricyclazole and of the commercial BEAM(TM) formulation. The analyses are carried out by ultra-high performance liquid chromatography technique coupled with high-resolution tandem mass spectrometry. Analysis of both tricyclazole and BEAM(TM) water solutions undergone to hydrolysis does not evidence new chromatographic peaks with respect to the not treated solutions. On the contrary, analysis of the same samples subjected to sunlight irradiation shows a decreased intensity of tricyclazole signal and the presence of new chromatographic peaks. Two photodegradation products of tricyclazole have been identified, one of which has been also quantified, being the commercial standard available. The pattern is similar for the solutions of the standard fungicide and of the BEAM(TM) formulation. The results obtained from eco-toxicological tests show that toxicity of tricyclazole standard solutions is greater than that of the irradiated ones, whereas toxicity levels of all the BEAM(TM) solutions investigated (non-irradiated, irradiated, and hydrolyzed) are comparable and lower than those shown by tricyclazole standard solutions. Experiments performed in paddy water solution show that there is no difference in the degradation products formed.

  11. Rapid qualitative and quantitative analysis of proanthocyanidin oligomers and polymers by ultra-performance liquid chromatographytandem mass spectrometry (UPLC-MS/MS)

    USDA-ARS?s Scientific Manuscript database

    We developed a rapid method with ultra-performance liquid chromatographytandem mass spectrometry (UPLC-MS/MS) for the qualitative and quantitative analysis of plant proanthocyanidins (PAs) directly from crude plant extracts. The method utilizes a range of cone voltages to achieve the depolymeriza...

  12. Rapid extraction and determination of 25 bioactive constituents in Alpinia oxyphylla using microwave extraction with ultra high performance liquid chromatography with tandem mass spectrometry.

    PubMed

    Sun, Zhi; Kong, Xiangzhen; Zuo, Lihua; Kang, Jian; Hou, Lei; Zhang, Xiaojian

    2016-02-01

    A novel and rapid microwave extraction and ultra high performance liquid chromatography with tandem mass spectrometry method was developed and validated for the simultaneous determination of 25 bioactive constituents (including two new constituents) in Fructus Alpinia oxyphylla. The optimized conditions of the microwave extraction was a microwave power of 300 W, extraction temperature of 80°C, solvent-to-solid ratio of 30 mL/g and extraction time of 8 min. Separation was achieved on a Waters ACQUITY UPLC(®) HSS C18 column (2.1 mm× 50 mm, 1.8 μm) using gradient elution with a mobile phase consisting of acetonitrile and 1 mM ammonium acetate at a flow rate of 0.2 mL/min. This is the first report of the simultaneous determination of 25 bioactive constituents in Fructus Alpinia oxyphylla by ultra high performance liquid chromatography with tandem mass spectrometry. The method was validated with good linearity, acceptable precision and accuracy. The validated method was successfully applied to determine the contents of 25 bioactive constituents in Fructus Alpinia oxyphylla from different sources and the analysis results were classified by hierarchical cluster analysis, which indicated the effect of different cultivation regions on the contents of constituents. This study provides powerful and practical guidance in the quality control of Alpinia oxyphylla and lays the foundation for further research of Alpinia oxyphylla. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Determination of Fusarium toxins in functional vegetable milks applying salting-out-assisted liquid-liquid extraction combined with ultra-high-performance liquid chromatography tandem mass spectrometry.

    PubMed

    Hamed, Ahmed M; Arroyo-Manzanares, Natalia; García-Campaña, Ana M; Gámiz-Gracia, Laura

    2017-11-01

    Vegetable milks are considered as functional foods due to their physiological benefits. Although the consumption of these products has significantly increased, they have received little attention in legislation with regard to contaminants. However, they may contain mycotoxins resulting from the use of contaminated raw materials. In this work, ultra-high-performance liquid chromatography tandem mass spectrometry has been proposed for the determination of the most relevant Fusarium toxins (fumonisin B 1 and B 2 , HT-2 and T-2 toxins, zearalenone, deoxynivalenol and fusarenon-X) in different functional beverages based on cereals, legumes and seeds. Sample treatment consisted of a simple salting-out-assisted liquid-liquid extraction with no further clean-up. The method provided limits of quantification between 3.2 and 57.7 µg L -1 , recoveries above 80% and precision with RSD lower than 12%. The method was also applied for studying the occurrence of these mycotoxins in market samples of vegetable functional beverages and deoxynivalenol was found in three oat-based commercial drinks.

  14. Quantitation of phlorizin and phloretin using an ultra high performance liquid chromatography-electrospray ionization tandem mass spectrometric method.

    PubMed

    Lijia, Xu; Guo, Jianru; Chen, QianQian; Baoping, Jiang; Zhang, Wei

    2014-06-01

    A sensitive and selective ultra high performance liquid chromatography-tandem mass spectrometric (UHPLC-MS/MS) method for the determination of phlorizin and phloretin in human plasma has been firstly developed. Samples were prepared after protein precipitation and analyzed on a C18 column interfaced with a triple quadrupole tandem mass spectrometer. Negative electrospray ionization was employed as the ionization source. The mobile phase consisted of acetonitrile-water (0.02% formic acid), using a gradient procedure. The analytes and internal standard dihydroquercetin were both detected by use of multiple reaction monitoring mode. The method was linear in the concentration range of 2.5-1000.0 ng/mL. The lower limit of quantification (LLOQ) was 2.5 ng/mL. The intra- and inter-day relative standard deviation across three validation runs over the entire concentration range was less than 9.2%. The accuracy determined at three concentrations was within ± 7.3% in terms of relative error. The total run time was 12.0 min. This assay offers advantages in terms of expediency, and suitability for the analysis of phlorizin and phloretin in various biological fluids. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. The utility of ultra-high performance supercritical fluid chromatography-tandem mass spectrometry (UHPSFC-MS/MS) for clinically relevant steroid analysis.

    PubMed

    Storbeck, Karl-Heinz; Gilligan, Lorna; Jenkinson, Carl; Baranowski, Elizabeth S; Quanson, Jonathan L; Arlt, Wiebke; Taylor, Angela E

    2018-05-15

    Liquid chromatography tandem mass spectrometry (LC-MS/MS) assays are considered the reference standard for serum steroid hormone analyses, while full urinary steroid profiles are only achievable by gas chromatography (GC-MS). Both LC-MS/MS and GC-MS have well documented strengths and limitations. Recently, commercial ultra-high performance supercritical fluid chromatography-tandem mass spectrometry (UHPSFC-MS/MS) systems have been developed. These systems combine the resolution of GC with the high-throughput capabilities of UHPLC. Uptake of this new technology into research and clinical labs has been slow, possibly due to the perceived increase in complexity. Here we therefore present fundamental principles of UHPSFC-MS/MS and the likely applications for this technology in the clinical research setting, while commenting on potential hurdles based on our experience to date. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

  16. A selective biomarker for confirming nitrofurazone residues in crab and shrimp using ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhang, Shuai; Guo, Yuanming; Yan, Zhongyong; Sun, Xiumei; Zhang, Xiaojun

    2015-12-01

    Reliably detecting nitrofurazone (NFZ) residues in farmed crab and shrimp was previously hindered by lack of appropriately specific analytical methodology. Parent NFZ rapidly breaks down in meat, and the commonly used side-chain metabolite, semicarbazide (SEM), is non-specific as it occurs naturally in crustacean shell often leading to 'false positive' detections in meat. Using 5-nitro-2-furaldehyde (NF) as marker metabolite, following pre-column derivatization with 2,4-dinitrophenylhydrazine (DNPH), ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) analysis in negative electrospray ionization mode enabled confirmation of NFZ residues in deliberately treated whole crab, crab meat and shrimp meat, with a limit of detection (LOD) and limit of quantification (LOQ) below 1 ng g(-1). Meanwhile, the derivatives of DNPH-NF were synthesized for the first time, purified by preparative liquid chromatography and structure characterized with nuclear magnetic resonance spectroscopy ((1)H-NMR). The purity of derivative was checked by ultra-performance liquid chromatography-tunable ultraviolet (UPLC-TUV), and the contents were beyond 99.9%. For comparison purposes, crustacean samples were analysed using both NF and SEM marker metabolites. NFZ treatment was revealed by both NF and SEM marker metabolites, but untreated crab also showed measurable levels of SEM which could potentially be misinterpreted as evidence of illegal NFZ use.

  17. Rapid separation and characterization of diterpenoid alkaloids in processed roots of Aconitum carmichaeli using ultra high performance liquid chromatography coupled with hybrid linear ion trap-Orbitrap tandem mass spectrometry.

    PubMed

    Xu, Wen; Zhang, Jing; Zhu, Dayuan; Huang, Juan; Huang, Zhihai; Bai, Junqi; Qiu, Xiaohui

    2014-10-01

    The lateral root of Aconitum carmichaeli, a popular traditional Chinese medicine, has been widely used to treat rheumatic diseases. For decades, diterpenoid alkaloids have dominated the phytochemical and biomedical research on this plant. In this study, a rapid and sensitive method based on ultra high performance liquid chromatography coupled with linear ion trap-Orbitrap tandem mass spectrometry was developed to characterize the diterpenoid alkaloids in Aconitum carmichaeli. Based on an optimized chromatographic condition, more than 120 diterpenoid alkaloids were separated with good resolution. Using a systematic strategy that combines high resolution separation, highly accurate mass measurements and a good understanding of the diagnostic fragment-based fragmentation patterns, these diterpenoid alkaloids were identified or tentatively identified. The identification of these chemicals provided essential data for further phytochemical studies and toxicity research of Aconitum carmichaeli. Moreover, the ultra high performance liquid chromatography with linear ion trap-Orbitrap mass spectrometry platform was an effective and accurate tool for rapid qualitative analysis of secondary metabolite productions from natural resources. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. A multiresidue approach for the simultaneous quantification of antibiotics in macroalgae by ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Leston, Sara; Freitas, Andreia; Rosa, João; Barbosa, Jorge; Lemos, Marco F L; Pardal, Miguel Ângelo; Ramos, Fernando

    2016-10-15

    Together with fish, algae reared in aquaculture systems have gained importance in the last years, for many purposes. Besides their use as biofilters of effluents, macroalgae's rich nutritional profiles have increased their inclusion in human diets but also in animal feeds as sources of fatty acids, especially important for the fish industry. Nonetheless, algae are continuously exposed to environmental contaminants including antibiotics and possess the ability for bioaccumulation of such compounds. Therefore, the present paper describes the development and validation of an ultra-high performance liquid chromatography with tandem mass spectrometry (UPLC-MS/MS) method for the simultaneous quantification of antibiotics in the green macroalgae Ulva lactuca. This multi-residue method enables the determination of 38 compounds distributed between seven classes and was fully validated according to EU Decision 2002/657/EC. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Simultaneous Determination of Food-Related Biogenic Amines and Precursor Amino Acids Using in Situ Derivatization Ultrasound-Assisted Dispersive Liquid-Liquid Microextraction by Ultra-High-Performance Liquid Chromatography Tandem Mass Spectrometry.

    PubMed

    He, Yongrui; Zhao, Xian-En; Wang, Renjun; Wei, Na; Sun, Jing; Dang, Jun; Chen, Guang; Liu, Zhiqiang; Zhu, Shuyun; You, Jinmao

    2016-11-02

    A simple, rapid, sensitive, selective, and environmentally friendly method, based on in situ derivatization ultrasound-assisted dispersive liquid-liquid microextraction (in situ DUADLLME) coupled with ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) using multiple reaction monitoring (MRM) mode has been developed for the simultaneous determination of food-related biogenic amines and amino acids. A new mass-spectrometry-sensitive derivatization reagent 4'-carbonyl chloride rosamine (CCR) was designed, synthesized, and first reported. Parameters and conditions of in situ DUADLLME and UHPLC-MS/MS were optimized in detail. Under the optimized conditions, the in situ DUADLLME was completed speedily (within 1 min) with high derivatization efficiencies (≥98.5%). With the cleanup and concentration of microextraction step, good analytical performance was obtained for the analytes. The results showed that this method was accurate and practical for quantification of biogenic amines and amino acids in common food samples (red wine, beer, wine, cheese, sausage, and fish).

  20. Determination of type A trichothecenes in coix seed by magnetic solid-phase extraction based on magnetic multi-walled carbon nanotubes coupled with ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Dong, Maofeng; Si, Wenshuai; Wang, Weimin; Bai, Bing; Nie, Dongxia; Song, Weiguo; Zhao, Zhihui; Guo, Yirong; Han, Zheng

    2016-09-01

    Magnetic solid-phase extraction (m-SPE) is a promising sample preparation approach due to its convenience, speed, and simplicity. For the first time, a rapid and reliable m-SPE approach using magnetic multi-walled carbon nanotubes (m-MWCNTs) as the adsorbent was proposed for purification of type A trichothecenes including T-2 toxins (T2), HT-2 toxins (HT-2), diacetoxyscirpenol (DAS), and neosolaniol (NEO) in coix seed. The m-MWCNTs were synthesized by assembling the magnetic nanoparticles (Fe3O4) with MWCNTs by sonication through an aggregation wrap mechanism, and characterized by transmission electron microscope. Several key parameters affecting the performance of the procedure were extensively investigated including extraction solutions, desorption solvents, and m-MWCNT amounts. Under the optimal sample preparation conditions followed by analysis with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), high sensitivity (limit of quantification in the range of 0.3-1.5 μg kg(-1)), good linearity (R (2) > 0.99), satisfactory recovery (73.6-90.6 %), and acceptable precision (≤2.5 %) were obtained. The analytical performance of the developed method has also been successfully evaluated in real coix seed samples. Graphical Abstract Flow chart of determination of type A trichothecenes in coix seed by magnetic solid-phase extraction coupled with ultra-high performance liquid chromatography-tandem mass spectrometry.

  1. Confirmation of congenital adrenal hyperplasia by adrenal steroid profiling of filter paper dried blood samples using ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Rossi, Claudia; Calton, Lisa; Brown, Heather A; Gillingwater, Scott; Wallace, A Michael; Petrucci, Francesca; Ciavardelli, Domenico; Urbani, Andrea; Sacchetta, Paolo; Morris, Michael

    2011-04-01

    The specificity of screening for congenital adrenal hyperplasia by direct measurement of 17-hydroxyprogesterone in filter paper dried blood spot samples by immunoassay is low and has a high false-positive rate. In order to reduce the false-positive rate of this test, we developed a rapid, robust, specific confirmatory procedure in which cortisol, 4-androstene-3,17-dione and 17-hydroxyprogesterone were measured simultaneously by ultra-performance liquid chromatography-tandem mass spectrometry. After extraction, samples were analysed by ultra-performance liquid chromatography-tandem mass spectrometry and 17-hydroxyprogesterone was quantified accurately. Other steroids were determined using stable deuterated internal standards. In total, 25 patient blood spot samples and 92 control samples were analysed. The assay was linear for 17-hydroxyprogesterone, with a coefficient of determination >0.997 and imprecision ≤ 6.5%. An upper limit of normal for 17-hydroxyprogester-one of 4.45 nmol/L was established by analysing a cohort of samples from unaffected newborns. In addition, a cut-off of 3.5 for the peak areas ratio (17-hydroxyprogesterone+4-androstene-3,17-dione)/cortisol, allows confirmation of the affected steroidogenic enzyme. A high throughput method for the detection of steroids related to congenital adrenal hyperplasia has been developed, allowing the false-positive rate associated with screening for 17-hydroxyprogesterone by immunoassay to be determined.

  2. [Determination of thyreostats in bovine urine using ultra-high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Lech, Rodziewicz; Jolanta, MasŁOwiecka; Anna, Sadowska; Halina, Car

    2017-10-08

    Five thyreostats (TSs), namely tapazole, thiouracil, methylthiouracil, propylthiouracil, and phenylthiouracil, were determined in bovine urine using ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) in positive electrospray ionization mode. Extraction and clean-up were achieved using a ChemElut cartridge with tert -butyl methyl ether, without a derivatization step. Separation was achieved on an Acquity UPLC SS T3 column. The mobile phase was acetonitrile and water containing 0.2% (v/v) formic acid. The mass spectrometer was operated in multiple reaction monitoring mode. Urine samples were spiked with TS solution at levels corresponding to 5, 10, 15, and 20 μg/L. The accuracy (internal standard corrected) ranged from 92% to 107%, with a repeatability precision (relative standard deviation, RSD) less than 15% for all five analytes. The RSDs within-laboratory reproducibility was less than 26%. The decision limits (CCα) and detection capabilities (CCβ) were obtained from a calibration curve and were in the ranges of 3.1-6.1 μg/L and 4.0-7.4 μg/L, respectively. The CCα and CCβ values were below the recommended concentration, which was set at 10 μg/L. The results show that the described method is suitable for the direct detection of TSs in bovine urine. This method can also be used to determine TSs in porcine urine.

  3. Determination of anthelmintic drug residues in milk using ultra high performance liquid chromatography-tandem mass spectrometry with rapid polarity switching.

    PubMed

    Whelan, Michelle; Kinsella, Brian; Furey, Ambrose; Moloney, Mary; Cantwell, Helen; Lehotay, Steven J; Danaher, Martin

    2010-07-02

    A new UHPLC-MS/MS (ultra high performance liquid chromatography coupled to tandem mass spectrometry) method was developed and validated to detect 38 anthelmintic drug residues, consisting of benzimidazoles, avermectins and flukicides. A modified QuEChERS-type extraction method was developed with an added concentration step to detect most of the analytes at <1 microg kg(-1) levels in milk. Anthelmintic residues were extracted into acetonitrile using magnesium sulphate and sodium chloride to induce liquid-liquid partitioning followed by dispersive solid phase extraction for cleanup. The extract was concentrated into dimethyl sulphoxide, which was used as a keeper to ensure analytes remain in solution. Using rapid polarity switching in electrospray ionisation, a single injection was capable of detecting both positively and negatively charged ions in a 13 min run time. The method was validated at two levels: the unapproved use level and at the maximum residue level (MRL) according to Commission Decision (CD) 2002/657/EC criteria. The decision limit (CCalpha) of the method was in the range of 0.14-1.9 and 11-123 microg kg(-1) for drugs validated at unapproved and MRL levels, respectively. The performance of the method was successfully verified for benzimidazoles and levamisole by participating in a proficiency study.

  4. A simple, rapid and novel method based on salting-out assisted liquid-liquid extraction for ochratoxin A determination in beer samples prior to ultra-high performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Mariño-Repizo, Leonardo; Goicoechea, Hector; Raba, Julio; Cerutti, Soledad

    2018-06-07

    A novel, simple, easy and cheap sample treatment strategy based on salting-out assisted liquid-liquid extraction (SALLE) for ochratoxin A (OTA) ultra-trace analysis in beer samples using ultra-high performance liquid chromatography-tandem mass spectrometry determination was developed. The factors involved in the efficiency of pretreatment were studied employing factorial design in the screening phase and the optimal conditions of the significant variables on the analytical response were evaluated using a central composite face-centred design (CCF). Consequently, the amount of salt ((NH 4 ) 2 SO 4 ), together with the volumes of sample, hydrophilic (acetone) and nonpolar (toluene) solvents, and times of vortexing and centrifugation were optimized. Under optimized conditions, the limits of detection (LOD) and quantification (LOQ) were 0.02 µg l -1 and 0.08 µg l -1 respectively. OTA extraction recovery by SALLE was approximately 90% (0.2 µg l -1 ). Furthermore, the methodology was in agreement with EU Directive requirements and was successfully applied for analysis of beer samples.

  5. Validation of a method for simultaneous determination of nitroimidazoles, benzimidazoles and chloramphenicols in swine tissues by ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Xia, Xi; Wang, Yuanyuan; Wang, Xia; Li, Yun; Zhong, Feng; Li, Xiaowei; Huang, Yaoling; Ding, Shuangyang; Shen, Jianzhong

    2013-05-31

    This paper presents a sensitive and confirmatory multi-residue method for the analysis of 23 veterinary drugs and metabolites belonging to three classes (nitroimidazoles, benzimidazoles, and chloramphenicols) in porcine muscle, liver, and kidney. After extracted with ethyl acetate and basic ethyl acetate sequentially, the crude extracts were defatted with hexane and further purified using Oasis MCX solid-phase extraction cartridges. Rapid determination was carried out by ultra-high performance liquid chromatography-electrospray ionization tandem mass spectrometry. Data acquisition was performed under positive and negative mode simultaneously. Recoveries based on matrix-matched calibrations for meat, liver, and kidney ranged from 50.6 to 108.1%. The method quantification limits were in the range of 3-100ng/kg. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. Solid-phase extraction in combination with dispersive liquid-liquid microextraction and ultra-high performance liquid chromatography-tandem mass spectrometry analysis: the ultra-trace determination of 10 antibiotics in water samples.

    PubMed

    Liang, Ning; Huang, Peiting; Hou, Xiaohong; Li, Zhen; Tao, Lei; Zhao, Longshan

    2016-02-01

    A novel method, solid-phase extraction combined with dispersive liquid-liquid microextraction (SPE-DLLME), was developed for ultra-preconcentration of 10 antibiotics in different environmental water samples prior to ultra-high performance liquid chromatography-tandem mass spectrometry detection. The optimized results were obtained as follows: after being adjusted to pH 4.0, the water sample was firstly passed through PEP-2 column at 10 mL min(-1), and then methanol was used to elute the target analytes for the following steps. Dichloromethane was selected as extraction solvent, and methanol/acetonitrile (1:1, v/v) as dispersive solvent. Under optimal conditions, the calibration curves were linear in the range of 1-1000 ng mL(-1) (sulfamethoxazole, cefuroxime axetil), 5-1000 ng mL(-1) (tinidazole), 10-1000 ng mL(-1) (chloramphenicol), 2-1000 ng mL(-1) (levofloxacin oxytetracycline, doxycycline, tetracycline, and ciprofloxacin) and 1-400 ng mL(-1) (sulfadiazine) with a good precision. The LOD and LOQ of the method were at very low levels, below 1.67 and 5.57 ng mL(-1), respectively. The relative recoveries of the target analytes were in the range from 64.16% to 99.80% with relative standard deviations between 0.7 and 8.4%. The matrix effect of this method showed a great decrease compared with solid-phase extraction and a significant value of enrichment factor (EF) compared with dispersive liquid-liquid microextraction. The developed method was successfully applied to the extraction and analysis of antibiotics in different water samples with satisfactory results.

  7. An efficient approach to identify different chemical markers between fibrous root and rhizome of Anemarrhena asphodeloides by ultra high-performance liquid chromatography quadrupole time-of-flight tandem mass spectrometry with multivariate statistical analysis.

    PubMed

    Wang, Fang-Xu; Yuan, Jian-Chao; Kang, Li-Ping; Pang, Xu; Yan, Ren-Yi; Zhao, Yang; Zhang, Jie; Sun, Xin-Guang; Ma, Bai-Ping

    2016-09-10

    An ultra high-performance liquid chromatography quadrupole time-of-flight tandem mass spectrometry approach coupled with multivariate statistical analysis was established and applied to rapidly distinguish the chemical differences between fibrous root and rhizome of Anemarrhena asphodeloides. The datasets of tR-m/z pairs, ion intensity and sample code were processed by principal component analysis and orthogonal partial least squares discriminant analysis. Chemical markers could be identified based on their exact mass data, fragmentation characteristics, and retention times. And the new compounds among chemical markers could be isolated rapidly guided by the ultra high-performance liquid chromatography quadrupole time-of-flight tandem mass spectrometry and their definitive structures would be further elucidated by NMR spectra. Using this approach, twenty-four markers were identified on line including nine new saponins and five new steroidal saponins of them were obtained in pure form. The study validated this proposed approach as a suitable method for identification of the chemical differences between various medicinal parts in order to expand medicinal parts and increase the utilization rate of resources. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Ultra-performance liquid chromatography-tandem mass spectrometry for the determination of atypical antipsychotics and some metabolites in in vitro samples.

    PubMed

    Li, Kun-Yan; Zhou, Yan-Gang; Ren, Hua-Yi; Wang, Feng; Zhang, Bi-Kui; Li, Huan-De

    2007-05-01

    The ultra-performance liquid chromatography-electrospray tandem mass spectrometry (UPLC-ESI-MS/MS) method has been developed to perform the determination of quetiapine, perospirone, aripiprazole and quetiapine sulfoxide in in vitro samples in less than 3 min. The UPLC separation was carried out using an Acquity UPLC BEH C18 column (100 mm x 2.1mm i.d., 1.7 microm particle size) that provided high efficiency and resolution in combination with high linear velocities. The UPLC system was coupled to a Waters Micromass Quattro Premier XE tandem quadrupole mass spectrometer. This system permits high-speed data acquisition without peak intensity degradation, and produces sharp and narrow chromatographic peaks (w(h) about 2.5s) of compounds. The determination was performed in multiple reaction monitoring (MRM) mode. The quantification parameters of the developed method were established, obtaining instrumental LODs lower than 0.005 microg/l and a repeatability at a low concentration level lower than 10% CV (n=10). Finally, the method was successfully applied to the analysis of atypical antipsychotics and some metabolites in in vitro samples.

  9. Ultra-performance liquid chromatography tandem mass-spectrometry (uplc-ms/ms) for the rapid, simultaneous analysis of thiamin, riboflavin, flavin adenine dinucleotide, nicotinamide and pyridoxal in human milk

    USDA-ARS?s Scientific Manuscript database

    A novel, rapid and sensitive Ultra Performance Liquid-Chromatography tandem Mass-Spectrometry (UPLC-MS/MS) method for the simultaneous determination of several B-vitamins in human milk was developed. Resolution by retention time or multiple reaction monitoring (MRM) for thiamin, riboflavin, flavin a...

  10. Multidetection of antibiotics in liver tissue by ultra-high-pressure-liquid-chromatography-tandem mass spectrometry.

    PubMed

    Freitas, Andreia; Barbosa, Jorge; Ramos, Fernando

    2015-01-22

    A multiresidue quantitative screening method covering 39 antibiotics from 7 different families by ultra-high-pressure-liquid-chromatography-tandem mass spectrometry (UHPLC-MS/MS) is described. Sulfonamides, trimethoprim, tetracyclines, macrolides, quinolones, penicillins and chloramphenicol are simultaneously detected in liver tissue. A simple sample treatment method consisting of extraction with a mixture of acetonitrile and ethylenediaminetetraacetic acid (EDTA) followed by solid-phase extraction (SPE) with a hydrophilic-lipophilic balanced (HLB) cartridge was developed. The methodology was validated, in accordance with Decision 2002/657/EC, by evaluating the following required parameters: decision limit (CCα), detection capability (CCβ), specificity, repeatability and reproducibility. The precision, in terms of the relative standard deviation, was under 22% for all of the compounds, and the recoveries were between 80% and 110%. The CCα and CCβ were determined according to the maximum residue limit (MRL) or the minimum required performance limit (MRPL), when established. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. The use of ultra-high pressure liquid chromatography with tandem mass spectrometric detection of analysis of agrochemical residues and mycotoxines in food - challenges and applications

    USDA-ARS?s Scientific Manuscript database

    In the field of food contaminant analysis, the most significant development of recent years has been the integration of ultra-high pressure liquid chromatography (UHPLC), coupled to tandem quadrupole mass spectrometry (MS/MS), into analytical applications. In this review, we describe the emergence o...

  12. [Determination of 12 flavonoids in tobacco leaves using ultra-high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Li, Yong; Lin, Qian; Pang, Tao; Shi, Junli

    2015-07-01

    Flavonoids are very important secondary metabolites for tobacco plants. They are also considered as important flavor precursors for cigarettes. A method of ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established for the simultaneous determination of 12 flavonoids in tobacco leaves. The developed method determined 10 more flavonoids compared to the traditional method. A solution of methanol-water-chloroform (5:2:2, v/v/v) was used to extract the flavonoids from tobacco leaves and remove the pigment. Instrument analysis using the UPLC-MS/MS was completed in 13 min. The method validation was performed, and the results showed that the linear correlation coefficients (r2) of all the 12 flavonoids were more than 0.99. The limits of detection and the limits of quantification were in the range of 0.3-100 μg/L and 1.2-400 μg/L, respectively. Intra-day and Inter-day reproducibilities were in the range of 3.5%-7.4% and 5.2%-11.4%, respectively. The recoveries were 81.2%-111.9%. The established method was successfully used to analyze the flavonoids of tobacco leaves of 11 varieties. Significant concentration differences of the flavonoids were found among the determined varieties. Furthermore, significant positive correlation among the flavonoids with similar chemical structures (aglycones and their related glycosides, glycosides with the same aglycone, and similar aglycones) was found using the acquired data.

  13. Multi-residue determination of 210 drugs in pork by ultra-high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Yin, Zhiqiang; Chai, Tingting; Mu, Pengqian; Xu, Nana; Song, Yue; Wang, Xinlu; Jia, Qi; Qiu, Jing

    2016-09-09

    This paper presents a multi-residue analytical method for 210 drugs in pork using ultra-high-performance liquid chromatography-Q-Trap tandem mass spectrometry (UPLC-MS/MS) within 20min via positive ESI in scheduled multi-reaction monitoring (MRM) mode. The 210 drugs, belonging to 21 different chemical classes, included macrolides, sulfonamides, tetracyclines, β-lactams, β-agonists, aminoglycosides, antiviral drugs, glycosides, phenothiazine, protein anabolic hormones, non-steroidal anti-inflammatory drugs (NSAIDs), quinolones, antifungal drugs, corticosteroids, imidazoles, piperidines, piperazidines, insecticides, amides, alkaloids and others. A rapid and simple preparation method was applied to process the animal tissues, including solvent extraction with an acetonitrile/water mixture (80/20, v/v), defatting and clean-up processes. The recoveries ranged from 52% to 130% with relative standard deviations (RSDs)<20% for spiked concentrations of 10, 50 and 250μg/kg. More than 90% of the analytes achieved low limits of quantification (LOQs)<10μg/kg. The decision limit (CCα), detection capability (CCβ) values were in the range of 2-502μg/kg and 4-505μg/kg, respectively. This method is significant for food safety monitoring and controlling veterinary drug use. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Rapid determination of quinolones in cosmetic products by ultra high performance liquid chromatography with tandem mass spectrometry.

    PubMed

    Liu, Shao-Ying; Huang, Xi-Hui; Wang, Xiao-Fang; Jin, Quan; Zhu, Guo-Nian

    2014-05-01

    This study developed an improved analytical method for the simultaneous quantification of 13 quinolones in cosmetics by ultra high performance liquid chromatography combined with ESI triple quadrupole MS/MS under the multiple reaction monitoring mode. The analytes were extracted and purified by using an SPE cartridge. The limits of quantification ranged from 0.03 to 3.02 μg/kg. The precision for determining the quinolones was <19.39%. The proposed method was successfully developed for the determination of quinolones in real cosmetic samples. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Simultaneous determination of niacin and pyridoxine at trace levels by using diode array high-performance liquid chromatography and liquid chromatography with quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    Sel, Sabriye; Öztürk Er, Elif; Bakırdere, Sezgin

    2017-12-01

    A highly sensitive and simple diode-array high-performance liquid chromatography and liquid chromatography with quadrupole time-of-flight tandem mass spectrometry method was developed for the simultaneous determination of niacin and pyridoxine in pharmaceutical drugs, tap water, and wastewater samples. To determine the in vivo behavior of niacin and pyridoxine, analytes were subjected to simulated gastric conditions. The calibration plots of the diode-array high-performance liquid chromatography and liquid chromatography with quadrupole time-of-flight tandem mass spectrometry method showed good linearity over a wide concentration range with close to 1.0 correlation coefficients for both analytes. The limit of detection/limit of quantitation values for liquid chromatography quadrupole time-of-flight tandem mass spectrometry analysis were 1.98/6.59 and 1.3/4.4 μg/L for niacin and pyridoxine, respectively, while limit of detection/limit of quantitation values for niacin and pyridoxine in high-performance liquid chromatography analysis were 3.7/12.3 and 5.7/18.9 μg/L, respectively. Recovery studies were also performed to show the applicability of the developed methods, and percentage recovery values were found to be 90-105% in tap water and 94-97% in wastewater for both analytes. The method was also successfully applied for the qualitative and quantitative determination of niacin and pyridoxine in drug samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Sensitive analysis of blonanserin, a novel antipsychotic agent, in human plasma by ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Ogawa, Tadashi; Hattori, Hideki; Kaneko, Rina; Ito, Kenjiro; Iwai, Masayo; Mizutani, Yoko; Arinobu, Tetsuya; Ishii, Akira; Suzuki, Osamu; Seno, Hiroshi

    2010-01-01

    A rapid and sensitive method for analysis of blonanserin in human plasma by ultra-performance liquid chromatography-tandem mass spectrometry is presented. After pretreatment of a plasma sample by solid-phase extraction, blonanserin was analyzed by the system with a C(18) column. This method gave satisfactory recovery rates, reproducibility, and good linearity of calibration curve in the range of 0.01-10.0 ng/mL for quality control samples spiked with blonanserin. The detection limit was as low as 1 pg/mL. This method seems very useful in forensic and clinical toxicology and pharmacokinetic studies.

  17. Quality evaluation of Semen Cassiae (Cassia obtusifolia L.) by using ultra-high performance liquid chromatography coupled with mass spectrometry.

    PubMed

    Zhang, Wei-Dong; Wang, Ying; Wang, Qing; Yang, Wan-Jun; Gu, Yi; Wang, Rong; Song, Xiao-Mei; Wang, Xiao-Juan

    2012-08-01

    A sensitive and reliable ultra-high performance liquid chromatography-electrospray ionization-tandem mass spectrometry has been developed and partially validated to evaluate the quality of Semen Cassiae (Cassia obtusifolia L.) through simultaneous determination of 11 anthraquinones and two naphtha-γ-pyrone compounds. The analysis was achieved on a Poroshell 120 EC-C(18) column (100 mm × 2.1 mm, 2.7 μm; Agilent, Palo Alto, CA, USA) with gradient elution using a mobile phase that consisted of acetonitrile-water (30 mM ammonium acetate) at a flow rate of 0.4 mL/min. For quantitative analysis, all calibration curves showed perfect linear regression (r(2) > 0.99) within the testing range. This method was also validated with respect to precision and accuracy, and was successfully applied to quantify the 13 components in nine batches of Semen Cassiae samples from different areas. The performance of developed method was compared with that of conventional high-performance liquid chromatography method. The significant advantages of the former include high-speed chromatographic separation, four times faster than high-performance liquid chromatography with conventional columns, and great enhancement in sensitivity. This developed method provided a new basis for overall assessment on quality of Semen Cassiae. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Determination of steroid hormones in fish tissues by microwave-assisted extraction coupled to ultra-high performance liquid chromatography tandem mass spectrometry.

    PubMed

    Guedes-Alonso, Rayco; Sosa-Ferrera, Zoraida; Santana-Rodríguez, José Juan

    2017-12-15

    Steroid hormones produce adverse effects on biota as well as bioaccumulation in fish and seafood, making it necessary to develop methodologies to evaluate these compounds in samples related to the food chain. This work presents an analytical method for evaluating 15 steroid hormones in fish tissue. It is based on microwave-assisted extraction and solid-phase extraction coupled to ultra-high-performance liquid chromatography tandem mass spectrometry (MAE-SPE-UHPLC-MS/MS). The proposed method shows appropriate detection limits (0.14-49.0ngg -1 ), recoveries in the range of 50% and good repeatability. After optimization, the method was applied to different tissues from two small fishes of the Canary Islands that constitute an important level of the food web (Boops boops and Sphoeroides marmoratus) and were exposed to the outfall of the Las Palmas de Gran Canaria wastewater treatment plant. The concentrations of eight detected compounds ranged from below the quantification limits to 3.95μgg -1 . Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Lipid Identification by Untargeted Tandem Mass Spectrometry Coupled with Ultra-High-Pressure Liquid Chromatography.

    PubMed

    Gugiu, Gabriel B

    2017-01-01

    Lipidomics refers to the large-scale study of lipids in biological systems (Wenk, Nat Rev Drug Discov 4(7):594-610, 2005; Rolim et al., Gene 554(2):131-139, 2015). From a mass spectrometric point of view, by lipidomics we understand targeted or untargeted mass spectrometric analysis of lipids using either liquid chromatography (LC) (Castro-Perez et al., J Proteome Res 9(5):2377-2389, 2010) or shotgun (Han and Gross, Mass Spectrom Rev 24(3):367-412, 2005) approaches coupled with tandem mass spectrometry. This chapter describes the former methodology, which is becoming rapidly the preferred method for lipid identification owing to similarities with established omics workflows, such as proteomics (Washburn et al., Nat Biotechnol 19(3):242-247, 2001) or genomics (Yadav, J Biomol Tech: JBT 18(5):277, 2007). The workflow described consists in lipid extraction using a modified Bligh and Dyer method (Bligh and Dyer, Can J Biochem Physiol 37(8):911-917, 1959), ultra high pressure liquid chromatography fractionation of lipid samples on a reverse phase C18 column, followed by tandem mass spectrometric analysis and in silico database search for lipid identification based on MSMS spectrum matching (Kind et al., Nat Methods 10(8):755-758, 2013; Yamada et al., J Chromatogr A 1292:211-218, 2013; Taguchi and Ishikawa, J Chromatogr A 1217(25):4229-4239, 2010; Peake et al., Thermoscientifices 1-3, 2015) and accurate mass of parent ion (Sud et al., Nucleic Acids Res 35(database issue):D527-D532, 2007; Wishart et al., Nucleic Acids Res 35(database):D521-D526, 2007).

  20. Determination of naphthalene-derived compounds in apples by ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Esparza, X; Moyano, E; Cosialls, J R; Galceran, M T

    2013-06-11

    Naphthylacetic acid, naphthyloxy acetic acid and naphthylacetamide belong to a group of synthetic substances known as "auxin-like" compounds which are used as growth regulators in vegetables and fruits due to their structure similarities with the indoleacetic acid, the most important plant auxin. This paper reports a selective, sensitive and fast ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for the determination of naphthylacetamide (NAD) and the isomers (α and β) of naphthylacetic acid (NAA) and naphthyloxy acetic (NOA) acid in apple samples. A baseline separation between the respective isomers was achieved using an RP-Amide column with gradient elution. The UHPLC-MS/MS method developed, using electrospray and selected reaction monitoring (SRM) acquisition mode led to a reliable determination of these family of compounds in apple samples at low quantitation levels, down to 1.0 μg kg(-1) and 0.25 μg kg(-1) respectively. For confirmation of NAA accurate mass measurement is proposed giving at these conditions quantitation limits of 10 μg kg(-1) for this compound. The UHPLC-MS/MS method developed was used for the analysis of apple samples harvested in three different apple fields from Lleida (Spain) during the blooming period. NAD and NAA were found in samples collected during 4-5 weeks after application at concentrations between the quantification limits and 43 μg kg(-1) and 24 μg kg(-1), respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

  1. Study of the in vitro metabolism of TJ0711 using ultra high performance liquid chromatography with quadrupole time-of-flight and ultra fast liquid chromatography with quadrupole linear ion trap mass spectrometry.

    PubMed

    Hu, Lei; Lv, Zhenhua; Li, Gao; Xu, Xiaolong; Zhang, Chenghao; Cao, Peng; Huang, Jiangeng; Si, Luqin

    2015-06-01

    TJ0711 (1-[4-(2-methoxyethyl)phenoxy]-3-[2-(2-methoxyphenoxy)ethylamino]-2-propanol) is a novel β-adrenoreceptor blocker with vasodilating activity. The aim of this study was to investigate the in vitro metabolic properties of TJ0711 from both qualitative and quantitative aspects using mouse, rat, dog, and human liver microsomes as well as rat hepatocytes. Two modern liquid chromatography with tandem mass spectrometry systems, ultra high performance liquid chromatography with quadrupole time-of-flight mass spectrometry and ultra fast liquid chromatography with quadrupole linear ion trap mass spectrometry, were utilized for the analysis. To better characterize the metabolic pathways of TJ0711, two major metabolites were incubated under the same conditions as that for TJ0711. TJ0711 was extensively metabolized in vitro, and a total of 34 metabolites, including 19 phase I and 15 phase II metabolites, were identified. Similar metabolite profiles were observed among species, and demethylation, hydroxylation, carboxylic acid formation, and glucuronidation were proposed as the major metabolic routes. Significant interspecies differences were observed in the metabolic stability studies of TJ0711. Furthermore, gender differences were significant in mice, rats, and dogs, but were negligible in humans. The valuable information provided in this work will be useful in planning and interpreting further pharmacokinetic, in vivo metabolism and toxicological studies of this novel β-blocker. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Multiresidue analysis of sulfonamides, quinolones, and tetracyclines in animal tissues by ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhang, Zhiwen; Li, Xiaowei; Ding, Shuangyang; Jiang, Haiyang; Shen, Jianzhong; Xia, Xi

    2016-08-01

    A multiresidue method for the efficient identification and quantification of 38 compounds from 3 different classes of antibiotics (tetracyclines, sulfonamides, and quinolones) in animal tissues has been developed. The method optimization involved the selection of extraction solutions, comparison of different solid-phase extraction cartridges and different mobile phases. As a result, the samples were extracted with Mcllvaine and phosphate buffers, followed by clean-up step based on solid-phase extraction with Oasis HLB cartridge. All compounds were determined by ultra-high performance liquid chromatography-tandem mass spectrometry, in one single injection with a chromatographic run time of only 9min. The method efficiency was evaluated in 5 tissues including muscle, liver, and kidney, and the mean recoveries ranged from 54% to 102%, with inter-day relative standard deviation lower than 14%. The limits of quantification were between 0.5 and 10μg/kg, which were satisfactory to support future surveillance monitoring. The developed method was applied to the analysis of swine liver and chicken samples from local markets, and sulfamethazine was the most commonly detected compound in the animal samples, with the highest residue level of 998μg/kg. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Determination of 82 veterinary drugs in swine waste lagoon sludge by ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Li, Xiaowei; Guo, Ping; Shan, Yawen; Ke, Yuebin; Li, Hui; Fu, Qin; Wang, Yingyu; Liu, Tianhe; Xia, Xi

    2017-05-26

    This work reports the development of a multi-residue method for the identification and quantification of 82 veterinary drugs belonging to different chemical classes in swine waste lagoon. The proposed method applies a solid-phase extraction procedure with Oasis PRiME HLB cartridges that combines isolation of the compounds and sample clean-up in a single step. Analysis is performed by ultra-high performance liquid chromatography-tandem mass spectrometry, in one single injection with a chromatographic run time of only 9.5min. Linearity was studied in the range between 1 and 500μgkg -1 using standards prepared both in pure solvent and in the presence of matrix, showing coefficients of determination higher than 0.99 for all the analytes except for cefapirin in matrix. The average recoveries were in the range of 60-110% for most of the compounds tested with inter-day relative standard deviations below 17%. More than 97% of the investigated compounds had less or equal to a 5μgkg -1 quantitation limit in the studied matrix. Finally, the method was used with success to detect and quantify veterinary drugs residues in real samples with sulfonamides, quinolones, and tetracyclines being the most frequently determined compound groups. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Trace determination of organophosphate esters in white wine, red wine, and beer samples using dispersive liquid-liquid microextraction combined with ultra-high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Pang, Long; Yang, Huiqiang; Yang, Peijie; Zhang, Hongzhong; Zhao, Jihong

    2017-08-15

    In this study, dispersive liquid-liquid microextraction coupled with ultra-high-performance liquid chromatography-tandem mass spectrometry was developed for the analysis of five representative organophosphate esters (OPEs) in wine samples. Under optimized conditions, the proposed method resulted in good linearity (R 2 >0.9933) over the range of 0.1-100μgL -1 , with limits of detection (LODs, S/N =3) and quantification (LOQs, S/N =10) in the ranges of 0.48-18.8ngL -1 and 1.58-62.5ngL -1 , respectively. Inter- and intra-assay precisions of RSD% ranged from 3.21% to 6.13% and from 1.69% to 7.63%, respectively. The spiked recoveries of target OPEs from white wine, red wine, and beer samples were in the ranges of 80-122%, 76-120%, and 76-110%, respectively, at two different concentration levels. The total concentrations of five OPEs found in white wine, red wine, and beer samples were in the ranges of 0.29-0.85μgL -1 , 1.00-3.05μgL -1 , and 0.86-1.47μgL -1 , respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. [Separation and identification of 5 glycosidic flavor precursors in tobacco by ultra performance liquid chromatography-electrospray ionization tandem mass spectrometry].

    PubMed

    Wu, Xinhua; Zhu, Ruizhi; Ren, Zhuoying; Wang, Kai; Mou, Dingrong; Wei, Wanzhi; Miao, Mingming

    2009-11-01

    A qualitative method for the identification of 5 main glycosidic flavor precursors in tobacco was developed by using ultra performance liquid chromatography-electrospray ionization tandem mass spectrometry (UPLC-ESI MS/MS) and gas chromatography-mass spectrometry (GC-MS). The glycosidic flavor precursors in tobacco were extracted with methanol, cleaned up with an XAD-2 column. The aglycones were later released by enzyme-mediated hydrolysis under the condition of pH 5. The 5 volatile aglycone moieties were identified by GC-MS standard spectra library. The precursor ions of glycosides were determined by using electrospray ionization mass spectrometry in negative ion mode, then the 5 glycosidic flavor precursors were identified by using product ion scan (MS2) finally, using UPLC-ESI MS/MS, separation and identification of 5 glycosidic flavor precursors were accomplished on an RP-C,8 column in the multiple reaction monitoring (MRM) mode by using methanol and acetic acid-ammonium acetate aqueous solution as eluent. This work lays a foundation for the analysis of glycosidic flavor precursors without the standards by using liquid chromatography-mass spectrometry.

  6. Simultaneous determination of estrogens and progestogens in honey using high performance liquid chromatography-tandem mass spectrometry

    USDA-ARS?s Scientific Manuscript database

    This work describes the development and validation of a method for the simultaneous determination of 13 estrogens and progestogens in honey by high performance liquid chromatography-tandem mass spectrometry. The target compounds were preconcentrated by solid phase extraction. Pretreatment variables ...

  7. Comparative analysis of sixteen flavonoids from different parts of Sophora flavescens Ait. by ultra high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Weng, Zebin; Zeng, Fei; Zhu, Zhenhua; Qian, Dawei; Guo, Sheng; Wang, Hanqing; Duan, Jin-Ao

    2018-07-15

    The root of Sophora flavescens Ait. has long been used as a crude drug in China and other Asian countries for thousands of years. The quinolizidine alkaloids and flavonoids are considered as the main bioactive components in this plant. To determine the distribution and content of the flavonoids in different organs of this plant, a rapid, sensitive and reproducible method was established using ultra-high-performance liquid chromatography coupled with a triple quadrupole electrospray tandem mass spectrometry. A total of sixteen flavonoids including five different types (isoflavones, pterocarpans, flavones, flavonols and prenylflavonoids) were simultaneously determined in 10 min. The established method was fully validated in terms of linearity, sensitivity, precision, repeatability as well as recovery and successfully applied in the methanolic extracts of S. flavescens parts (root, stem, leaf, pod and seed). The analysis results indicated that the distribution and contents of different type of flavonoids showed remarkable differences among the five organs of S. flavescens. This study might be useful for the rational utilization of S. flavescens resource. Copyright © 2018 Elsevier B.V. All rights reserved.

  8. Evaluating the Antibacterial Properties of Polyacetylene and Glucosinolate Compounds with Further Identification of Their Presence within Various Carrot (Daucus carota) and Broccoli (Brassica oleracea) Cultivars Using High-Performance Liquid Chromatography with a Diode Array Detector and Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry Analyses.

    PubMed

    Hinds, L; Kenny, O; Hossain, M B; Walsh, D; Sheehy, E; Evans, P; Gaffney, M; Rai, D K

    2017-08-23

    Ongoing consumer concerns over using synthetic additives in foods has strongly influenced efforts worldwide to source suitable natural alternatives. In this study, the antibacterial efficacy of polyacetylene and glucosinolate compounds was evaluated against both Gram positive and Gram negative bacterial strains. Falcarinol [minimum inhibitory concentration (MIC) = 18.8-37.6 μg/mL] demonstrated the best overall antibacterial activity, while sinigrin (MIC = 46.9-62.5 μg/mL) was the most active glucosinolate compound. High-performance liquid chromatography with a diode array detector analysis showed falcarinol [85.13-244.85 μg/g of dry weight (DW)] to be the most abundant polyacetylene within six of the eight carrot (Daucus carota) cultivars investigated. Meanwhile, sinigrin (100.2-244.3 μg/g of DW) was the most abundant glucosinolate present within the majority of broccoli (Brassica oleracea) cultivars investigated using ultra performance liquid chromatography-tandem mass spectrometry analysis. The high abundance of both falcarinol and sinigrin within these respective species suggests that they could serve as potential sources of natural antibacterial agents for use as such in food products.

  9. Multi-target determination of organic ultraviolet absorbents in organism tissues by ultrasonic assisted extraction and ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Peng, Xianzhi; Jin, Jiabin; Wang, Chunwei; Ou, Weihui; Tang, Caiming

    2015-03-06

    A sensitive and reliable method was developed for multi-target determination of 13 most widely used organic ultraviolet (UV) absorbents (including UV filters and UV stabilizers) in aquatic organism tissues. The organic UV absorbents were extracted using ultrasonic-assisted extraction, purified via gel permeation chromatography coupled with silica gel column chromatography, and determined by ultra-high performance liquid chromatography-tandem mass spectrometry. Recoveries of the UV absorbents from organism tissues mostly ranged from 70% to 120% from fish filet with satisfactory reproducibility. Method quantification limits were 0.003-1.0ngg(-1) dry weight (dw) except for 2-ethylhexyl 4-methoxycinnamate. This method has been applied to analysis of the UV absorbents in wild and farmed aquatic organisms collected from the Pearl River Estuary, South China. 2-Hydroxy-4-methoxybenzophenone and UV-P were frequently detected in both wild and farmed marine organisms at low ngg(-1)dw. 3-(4-Methylbenzylidene)camphor and most of the benzotriazole UV stabilizers were also frequently detected in maricultured fish. Octocrylene and 2-ethylhexyl 4-methoxycinnamate were not detected in any sample. This work lays basis for in-depth study about bioaccumulation and biomagnification of the UV absorbents in marine environment. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Determination of caramel colorants' by-products in liquid foods by ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS).

    PubMed

    Goscinny, Séverine; Hanot, Vincent; Trabelsi, Hasna; Van Loco, Joris

    2014-01-01

    2-Methylimidazole, 4-methylimidazole (2-MI and 4-MI), 2-acetyl-4-(1,2,3,4-tetrahydroxybutyl) imidazole (THI) and 5-hydroxymethylfurfural (5-HMF) are neo-formed compounds generated during the manufacture of caramel colours and are transferred to the processed food. These contaminants are known to have a toxicological profile that may pose health risks. Hence, to characterise THI, 2- and 4-MI and 5-HMF levels in liquid foods, an ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was developed and sample preparation was divided into two analytical strategies depending on the concentration range expected in the type of foods targeted. For the determination of the imidazole substitutes (THI, 2- and 4-MI), a sample enrichment and clean-up step by strong cation solid-phase extraction was developed. This method is capable of quantifying over a range of 5 ng ml⁻¹ (LOQ) to 500 ng ml⁻¹ with recoveries of 75.4-112.4% and RSDs of 1.5-15%. For determination of 5-HMF, a standard addition method was applied covering the linear range of 0.25-30 µg ml⁻¹ with RSDs from 2.8% (for intraday precision) to 9.2% (for intermediate precision). The validated analytical methods were applied to 28 liquid food samples purchased from local markets. THI was found only in the beer samples at levels up to 141.2 ng ml⁻¹. For 2-MI, non-quantifiable traces were observed for all samples, while 4-MI was observed in all samples with large concentration variations (from < LOQ to 563.9 ng ml⁻¹). 5-HMF was found at expected concentrations, except for a sherry vinegar sample (113 µg ml⁻¹), which required a high level of dilution before following the standard addition protocol.

  11. Environmental analysis of alcohol ethoxylates and nonylphenol ethoxylate metabolites by ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Lara-Martín, Pablo A; González-Mazo, Eduardo; Brownawell, Bruce J

    2012-03-01

    Surfactants and their metabolites can be found in aquatic environments at relatively high concentrations compared with other micropollutants due in part to the exceptionally large volumes produced every year. We have focused our attention here on the most widely used nonionic surfactants, alcohol ethoxylates (AEOs), and on nonylphenol ethoxylate (NPEO) degradation products (short-chain nonylphenol ethoxylates, NP1-3EO, nonylphenol, NP, and nonylphenol ethoxycarboxylates, NP1-2EC), which are endocrine-disrupting compounds. Our main objective in this work was to develop a methodology aimed at the extraction, isolation, and improved analysis of these analytes in environmental samples at trace levels. Extraction recoveries of target compounds were determined for sediment samples after ultrasonic extraction and purification using HLB or C18 solid-phase extraction minicolumns. Recovery percentages were usually between 61 and 102% but were lower for longer AEO ethoxymers. Identification and quantification of target compounds was carried out using a novel ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS-MS) approach, a combination that provides higher sensitivity and faster analysis than prior methods using conventional high-performance liquid chromatography-mass spectrometry. Limits of detection were usually below 0.5 ng/g, being higher for monoethoxylate species (>5 ng/g) because of poor ionization. The method was used for analyzing surface sediment samples collected at Jamaica Bay (NY) in 2008. The highest values (28,500 ng/g for NP, 4,200 ng/g for NP1-3EO, 22,400 ng/g for NP1-2EC, and 1,500 ng/g for AEOs) were found in a sampling station from a restricted water circulation area that is heavily impacted by wastewater discharges.

  12. A simple and rapid ultra-high-performance liquid chromatography-tandem mass spectrometry method to determine plasma biotin in hemodialysis patients.

    PubMed

    Yagi, Shigeaki; Nishizawa, Manabu; Ando, Itiro; Oguma, Shiro; Sato, Emiko; Imai, Yutaka; Fujiwara, Masako

    2016-08-01

    A simple, rapid, and selective method for determination of plasma biotin was developed using ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). After single-step protein precipitation with methanol, biotin and stable isotope-labeled biotin as an internal standard (IS) were chromatographed on a pentafluorophenyl stationary-phase column (2.1 × 100 mm, 2.7 μm) under isocratic conditions using 10 mm ammonium formate-acetonitrile (93:7, v/v) at a flow rate of 0.6 mL/min. The total chromatographic runtime was 5 min for each injection. Detection was performed in a positive electrospray ionization mode by monitoring selected ion transitions at m/z 245.1/227.0 and 249.1/231.0 for biotin and the IS, respectively. The calibration curve was linear in the range of 0.05-2 ng/mL using 300 μL of plasma. The intra- and inter-day precisions were all <7.1%. The accuracy varied from -0.7 to 8.2%. The developed UHPLC-MS/MS method was successfully applied to determine plasma biotin concentrations in hemodialysis patients. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  13. Biomonitoring of 21 endocrine disrupting chemicals in human hair samples using ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Rodríguez-Gómez, R; Martín, J; Zafra-Gómez, A; Alonso, E; Vílchez, J L; Navalón, A

    2017-02-01

    Rapid industrial growth has increased human exposure to a large variety of chemicals with adverse health effects. These industrial chemicals are usually present in the environment, foods, beverages, clothes and personal care products. Among these compounds, endocrine disrupting chemicals (EDCs) have raised concern over the last years. In the present work, the determination of 21 EDCs in human hair samples is proposed. An analytical method based on the digestion of the samples with a mixture of acetic acid/methanol (20:80, v/v) followed by a solid-liquid microextraction and analysis by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was developed and validated. The most influential parameters affecting the extraction method were optimized. The method was validated using matrix-matched calibration and recovery assays. Limits of detection ranged from 0.2 to 4 ng g -1 , limits of quantification from 0.5 to 12 ng g -1 , and inter- and intra-day variability was under 15% in all cases. Recovery rates for spiked samples ranged from 92.1 to 113.8%. The method was applied for the determination of the selected compounds in human hair. Samples were collected weekly from six randomly selected volunteers (three men and three women) over a three-month period. All the analyzed samples tested positive for at least one of the analyzed compounds. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. Determination of perfluorinated chemicals in food and drinking water using high-flow solid-phase extraction and ultra-high performance liquid chromatography/tandem mass spectrometry.

    PubMed

    Chang, Ying-Chia; Chen, Wen-Ling; Bai, Fang-Yu; Chen, Pau-Chung; Wang, Gen-Shuh; Chen, Chia-Yang

    2012-01-01

    For this study, we developed methods of determining ten perfluorinated chemicals in drinking water, milk, fish, beef, and pig liver using high-flow automated solid-phase extraction (SPE) and ultra-high performance liquid chromatography/tandem mass spectrometry. The analytes were separated on a core-shell Kinetex C18 column. The mobile phase was composed of methanol and 10-mM N-methylmorpholine. Milk was digested with 0.5 N potassium hydroxide in Milli-Q water, and was extracted with an Atlantic HLB disk to perform automated SPE at a flow rate ranged from 70 to 86 mL/min. Drinking water was directly extracted by the SPE. Solid food samples were digested in alkaline methanol and their supernatants were diluted and also processed by SPE. The disks were washed with 40% methanol/60% water and then eluted with 0.1% ammonium hydroxide in methanol. Suppression of signal intensity of most analytes by matrixes was lower than 50%; it was generally lower in fish and drinking water but higher in liver. Most quantitative biases and relative standard deviations were lower than 15%. The limits of detection for most analytes were sub-nanograms per liter for drinking water and sub-nanograms per gram for solid food samples. This method greatly shortened the time and labor needed for digestion, SPE, and liquid chromatography. This method has been applied to analyze 14 types of food samples. Perfluorooctanoic acid was found to be the highest among the analytes (median at 3.2-64 ng/g wet weight), followed by perfluorodecanoic acid (0.7-25 ng/g) and perfluorododecanoic acid (0.6-15 ng/g).

  15. Analysis of chloramphenicol residues in the macroalgae Ulva lactuca through ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS).

    PubMed

    Leston, Sara; Freitas, Andreia; Nunes, Margarida; Barbosa, Jorge; Pardal, Miguel Ângelo; Ramos, Fernando

    2015-02-15

    Antibiotic use is a well-described practice to promote animal health whether for prevention or treatment. Nonetheless, it can also cause a number of potentially harmful effects that dictate the need to implement regulation to assure a reduction of hazards to the consumers and the environment. Chloramphenicol (CAP) is a broad-spectrum antibacterial excluded from use in animal food production but despite this, reports of illegal use still persist. More recently, awareness has risen that the surrounding natural ecosystems can potentially be contaminated by pharmaceuticals and the extent of their effects in non-target organisms is already under the scope of researchers. To face the demanding new challenges a methodology for the determination of CAP in the green macroalgae Ulva lactuca by ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) was developed, optimized and fully validated following the guidelines of the EC Decision 2002/657. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. [Determination of arbutin in apple juice concentrate by ultra performance liquid chromatography with electrospray ionization tandem mass spectrometry].

    PubMed

    Kong, Xianghong; He, Qiang; Yue, Aishan; Wu, Shuangmin; Li, Jianhua

    2010-06-01

    An ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/ MS) method was developed for the determination of arbutin in apple juice concentrate. Samples were diluted with water, then cleaned-up with a PS-DVB column. Quantitation was carried out using an external standard method. UPLC was performed on an Eclipse Plus C, column (100 mm x 2.1 mm, 1.8 microm) using a gradient solvent system (methanol-water). MS/MS was performed with multiple reaction monitoring (MRM) mode. The detection limit of arbutin was 0.02 mg/L. The method showed good linear relationship at the range of 0.04-2.0 mg/L. The recoveries ranged from 75.2% to 102.7% with relative standard deviations (RSDs) less than 8.9%. The method is simple, fast and sensitive. It's suitable for quantitative and qualitative analysis of arbutin in apple juice concentrate.

  17. [Determination of 6 kinds of plant growth regulator in bean sprout by ultra high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Liu, Ping; Fan, Sai; Wu, Guohua; Zhao, Rong; Liu, Wei; Zhao, Xudong

    2016-05-01

    A method for the simultaneous determination of 6 plant growth regulator (PGR) residues in bean sprout was developed by ultra high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). 6-Benzylaminopurine, isopentennyladenine, 4-chlorophenoxyacetic acid, 4-fluorophenoxyacetic acid, indole-3- acetic acid and indole-3-butyric acid were concerned. Bean sprout samples were extracted by acetonitrile and QuEChERS extraction kit, purified by C18 powers. After centrifugation, the sample liquids was diluted 10 times by ultrapure water. The chromatographic analysis was carried out on an waters acquity UPLC BEH C18 column( 100 mm x 2.1 mm, 1.7 microm). The analyzer confirmed and quantified by mass spectrum of triple quadrupole in the multiple reaction monitoring (MRM) mode and quantified by matrix-matched external standard method. The calibration curves showed good linearity in each range with correlation coefficients greater than 0.998. 3 levels spiked recoveries were carried out using blank bean sprout extraction as substrate, the recoveries ranged from 84.2% to 107.5%, the relative standard deviations (RSDs) ranged from 3.08% to 12.71%. The qualitative limits of detections (S/N = 3) were 0.03-3.0 microg/kg and the quantitative limits(S/N = 10) were 0.1-10.0 microg/kg for the 6 PGRs. The method is simple and easy to operate, with less organic reagent, high sensitivity and good stability. It is suitable for the detection of 6 kinds of plant growth regulators in bean sprouts.

  18. Recent advances in ultra-high performance liquid chromatography for the analysis of traditional chinese medicine

    USDA-ARS?s Scientific Manuscript database

    Traditional Chinese medicines (TCMs) have been widely used for the prevention and treatment of various diseases for thousands of years in China. Ultra Performance Liquid Chromatography (UHPLC) is a relatively new technique offering new possibilities in liquid chromatography. This paper reviews recen...

  19. Dual ultrasonic-assisted dispersive liquid-liquid microextraction coupled with microwave-assisted derivatization for simultaneous determination of 20(S)-protopanaxadiol and 20(S)-protopanaxatriol by ultra high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhao, Xian-En; Lv, Tao; Zhu, Shuyun; Qu, Fei; Chen, Guang; He, Yongrui; Wei, Na; Li, Guoliang; Xia, Lian; Sun, Zhiwei; Zhang, Shijuan; You, Jinmao; Liu, Shu; Liu, Zhiqiang; Sun, Jing; Liu, Shuying

    2016-03-11

    This paper, for the first time, reported a speedy hyphenated technique of low toxic dual ultrasonic-assisted dispersive liquid-liquid microextraction (dual-UADLLME) coupled with microwave-assisted derivatization (MAD) for the simultaneous determination of 20(S)-protopanaxadiol (PPD) and 20(S)-protopanaxatriol (PPT). The developed method was based on ultra high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) detection using multiple-reaction monitoring (MRM) mode. A mass spectrometry sensitizing reagent, 4'-carboxy-substituted rosamine (CSR) with high reaction activity and ionization efficiency was synthesized and firstly used as derivatization reagent. Parameters of dual-UADLLME, MAD and UHPLC-MS/MS conditions were all optimized in detail. Low toxic brominated solvents were used as extractant instead of traditional chlorinated solvents. Satisfactory linearity, recovery, repeatability, accuracy and precision, absence of matrix effect and extremely low limits of detection (LODs, 0.010 and 0.015ng/mL for PPD and PPT, respectively) were achieved. The main advantages were rapid, sensitive and environmentally friendly, and exhibited high selectivity, accuracy and good matrix effect results. The proposed method was successfully applied to pharmacokinetics of PPD and PPT in rat plasma. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Ultra-high performance liquid chromatography tandem mass spectrometry for the determination of five glycopeptide antibiotics in food and biological samples using solid-phase extraction.

    PubMed

    Deng, Fenfang; Yu, Hong; Pan, Xinhong; Hu, Guoyuan; Wang, Qiqin; Peng, Rongfei; Tan, Lei; Yang, Zhicong

    2018-02-23

    This paper demonstrated the development and validation of an ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method for simultaneous determination of five glycopeptide antibiotics in food and biological samples. The target glycopeptide antibiotics were isolated from the samples by solvent extraction, and the extracts were cleaned with a tandem solid-phase extraction step using mixed strong cation exchange and hydrophilic/lipophilic balance cartridges. Subsequently, the analytes were eluted with different solvents, and then quantified by UHPLC-MS/MS in the positive ionization mode with multiple reaction monitoring. Under optimal conditions, good linear correlations were obtained for the five glycopeptide antibiotics in the concentration range of 1.0 μg/L to 20.0 μg/L, and with linear correlation coefficients >0.998. Employing this method, the target glycopeptide antibiotics in food and biological samples were identified with a recovery of 83.0-102%, and a low quantitation limit of 1.0 μg/kg in food and 2.0 μg/L in biological samples with low matrix effects. Copyright © 2018 Elsevier B.V. All rights reserved.

  1. Comparison of ultra-high performance supercritical fluid chromatography and ultra-high performance liquid chromatography for the separation of spirostanol saponins.

    PubMed

    Zhu, Ling-Ling; Zhao, Yang; Xu, Yong-Wei; Sun, Qing-Long; Sun, Xin-Guang; Kang, Li-Ping; Yan, Ren-Yi; Zhang, Jie; Liu, Chao; Ma, Bai-Ping

    2016-02-20

    Spirostanol saponins are important active components of some herb medicines, and their isolation and purification are crucial for the research and development of traditional Chinese medicines. We aimed to compare the separation of spirostanol saponins by ultra-high performance supercritical fluid chromatography (UHPSFC) and ultra-high performance liquid chromatography (UHPLC). Four groups of spirostanol saponins were separated respectively by UHPSFC and UHPLC. After optimization, UHPSFC was performed with a HSS C18 SB column or a Diol column and with methanol as the co-solvent. A BEH C18 column and mobile phase containing water (with 0.1% formic acid) and acetonitrile were used in UHPLC. We found that UHPSFC could be performed automatically and quickly. It is effective in separating the spirostanol saponins which share the same aglycone and vary in sugar chains, and is very sensitive to the number and the position of hydroxyl groups in aglycones. However, the resolution of spirostanol saponins with different aglycones and the same sugar moiety by UHPSFC was not ideal and could be resolved by UHPLC instead. UHPLC is good at differentiating the variation in aglycones, and is influenced by double bonds in aglycones. Therefore, UHPLC and UHPSFC are complementary in separating spirostanol saponins. Considering the naturally produced spirostanol saponins in herb medicines are different both in aglycones and in sugar chains, a better separation can be achieved by combination of UHPLC and UHPSFC. UHPSFC is a powerful technique for improving the resolution when UHPLC cannot resolve a mixture of spirostanol saponins and vice versa. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Ultra high performance liquid chromatography with tandem mass spectrometry screening and mutagenicity evaluation of photodegradation products of Carmoisine (E122) dye in a beverage.

    PubMed

    Yamjala, Karthik; Nainar, Meyyanathan Subramania; Ramisetti, Nageswara Rao

    2016-06-01

    The present study deals with the separation and identification of the photodegradation products formed when a commercial soft drink containing Carmoisine (E122) dye was exposed to natural sunlight. An ultra high performance liquid chromatography with quadrupole time-of-flight tandem mass spectrometry method was developed and validated to identify the unknown species of E122. During the study, it was observed that the dye decolourizes rapidly in beverage when compared to model standard solutions. The sunlight irradiation of beverage containing E122 resulted in four photodegradation products as identified by nontarget screening using high-resolution tandem mass spectrometry. Accurate mass measurements were used to identify the elemental composition, and to elucidate the structures of degradation products a software tool was employed. The degradation products (P1-P4) were formed from the interactions of the dye with other ingredients present in the beverage. The toxicity of the degradation products was evaluated on five bacterial strains (TA98, TA100, TA1535, TA1537, and WP2 uvrA pKM101) through an in vitro bacterial reverse mutation assay. The photodegradation products showed strong mutagenic potential in strain TA 100 (without S9) as detected by the Ames assay. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Determination of seven bisphenol analogues in reed and Callitrichaceae by ultra performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Lu, Libin; Yang, Yunjia; Zhang, Jing; Shao, Bing

    2014-03-15

    An analytical procedure was developed to simultaneously determine bisphenol S, bisphenol F, bisphenol B, bisphenol A, bisphenol AF, tetrachlorobisphenol A, and tetrabromobisphenol A in reed and Callitrichaceae. Homogenized samples were extracted with acetonitrile and purified using an ENVI™-Carb cartridge followed by an NH2 cartridge. The analytes were separated and quantified by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The recoveries at three fortified levels in reed and Callitrichaceae were 57-108% and 68-106%, respectively, with relative standard deviations of no more than 15% (n=6). The method limits of quantification and detection for the seven bisphenol analogues were 0.005-0.500μg/kg and 0.002-0.150μg/kg, respectively. This method was used to analyze the seven compounds in ten reed and Callitrichaceae samples collected from Zhejiang, China. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. High temperature-ultra performance liquid chromatography-mass spectrometry for the metabonomic analysis of Zucker rat urine.

    PubMed

    Gika, Helen G; Theodoridis, Georgios; Extance, Jon; Edge, Anthony M; Wilson, Ian D

    2008-08-15

    The applicability and potential of using elevated temperatures and sub 2-microm porous particles in chromatography for metabonomics/metabolomics was investigated using, for the first time, solvent temperatures higher than the boiling point of water (up to 180 degrees C) and thermal gradients to reduce the use of organic solvents. Ultra performance liquid chromatography, combined with mass spectrometry, was investigated for the global metabolite profiling of the plasma and urine of normal and Zucker (fa/fa) obese rats (a well established disease animal model). "Isobaric" high temperature chromatography, where the temperature and flow rate follow a gradient program, was developed and evaluated against a conventional organic solvent gradient. LC-MS data were first examined by established chromatographic criteria in order to evaluate the chromatographic performance and next were treated by special peak picking algorithms to allow the application of multivariate statistics. These studies showed that, for urine (but not plasma), chromatography at elevated temperatures provided better results than conventional reversed-phase LC with higher peak capacity and better peak asymmetry. From a systems biology point of view, better group clustering and separation was obtained with a larger number of variables of high importance when using high temperature-ultra performance liquid chromatography (HT-UPLC) compared to conventional solvent gradients.

  5. Fast and sensitive analysis of beta blockers by ultra-high-performance liquid chromatography coupled with ultra-high-resolution TOF mass spectrometry.

    PubMed

    Tomková, Jana; Ondra, Peter; Kocianová, Eva; Václavík, Jan

    2017-07-01

    This paper presents a method for the determination of acebutolol, betaxolol, bisoprolol, metoprolol, nebivolol and sotalol in human serum by liquid-liquid extraction and ultra-high-performance liquid chromatography coupled with ultra-high-resolution TOF mass spectrometry. After liquid-liquid extraction, beta blockers were separated on a reverse-phase analytical column (Acclaim RS 120; 100 × 2.1 mm, 2.2 μm). The total run time was 6 min for each sample. Linearity, limit of detection, limit of quantification, matrix effects, specificity, precision, accuracy, recovery and sample stability were evaluated. The method was successfully applied to the therapeutic drug monitoring of 108 patients with hypertension. This method was also used for determination of beta blockers in 33 intoxicated patients. Copyright © 2016 John Wiley & Sons, Ltd.

  6. Integration of electrochemistry with ultra-performance liquid chromatography/mass spectrometry.

    PubMed

    Cai, Yi; Zheng, Qiuling; Liu, Yong; Helmy, Roy; Loo, Joseph A; Chen, Hao

    2015-01-01

    This study presents the development of ultra-performance liquid chromatography (UPLC) mass spectrometry (MS) combined with electrochemistry (EC) for the first time and its application for the structural analysis of proteins/peptides that contain disulfide bonds. In our approach, a protein/peptide mixture sample undergoes a fast UPLC separation and subsequent electrochemical reduction in an electrochemical flow cell followed by online MS and tandem mass spectrometry (MS/MS) analyses. The electrochemical cell is coupled to the mass spectrometer using our recently developed desorption electrospray ionization (DESI) interface. Using this UPLC/EC/DESI-MS method, peptides that contain disulfide bonds can be differentiated from those without disulfide bonds, as the former are electroactive and reducible. MS/MS analysis of the disulfide-reduced peptide ions provides increased information on the sequence and disulfide-linkage pattern. In a reactive DESI- MS detection experiment in which a supercharging reagent was used to dope the DESI spray solvent, increased charging was obtained for the UPLC-separated proteins. Strikingly, upon online electrolytic reduction, supercharged proteins (e.g., α-lactalbumin) showed even higher charging, which will be useful in top- down protein structure MS analysis as increased charges are known to promote protein ion dissociation. Also, the separation speed and sensitivity are enhanced by approximately 1(~)2 orders of magnitude by using UPLC for the liquid chromatography (LC)/EC/MS platform, in comparison to the previously used high- performance liquid chromatography (HPLC). This UPLC/EC/DESI-MS method combines the power of fast UPLC separation, fast electrochemical conversion, and online MS structural analysis for a potentially valuable tool for proteomics research and bioanalysis.

  7. Rapid determination of yunaconitine and related alkaloids in aconites and aconite-containing drugs by ultra high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Song, Long; Zhang, Hong; Liu, Xin; Zhao, Zhi-Li; Chen, Shi-Lin; Wang, Zheng-Tao; Xu, Hong-Xi

    2012-12-01

    Yunaconitine (YAC) is a toxic aconite alkaloid that is considered to be a hidden aconite poison since it is frequently found in body fluids from aconite poisoning patients, but has not been well studied in commonly used herbal drugs. In this paper, a rapid and sensitive ultra high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) detection combined with microwave-assisted extraction (MAE) was developed for high throughput simultaneous determination of YAC and six other toxic aconite alkaloids in 31 samples of crude, processed aconites and aconite-containing drugs. The optimized method showed excellent linearity, precision, accuracy and recovery for all target compounds with short run time. YAC was detected in some samples with contents from 0.015 to 10.41 mg/g. This is the first report on the determination of YAC in Radix Aconiti, Radix Aconiti Kusnezoffii and aconite-containing drugs. This newly developed method facilitates the rapid screening of YAC and related toxic aconite alkaloids and allows YAC to be used as a chemical marker for the quality control of aconites and aconite-containing drugs. Copyright © 2012 John Wiley & Sons, Ltd.

  8. Analysis of lignans in Magnoliae Flos by turbulent flow chromatography with online solid-phase extraction and high-performance liquid chromatography with tandem mass spectrometry.

    PubMed

    Zhou, Xuan; Chen, Cen; Ye, Xiaolan; Song, Fenyun; Fan, Guorong; Wu, Fuhai

    2016-04-01

    In this study, a method coupling turbulent flow chromatography with online solid-phase extraction and high-performance liquid chromatography with tandem mass spectrometry was developed for analyzing the lignans in Magnoliae Flos. By the online pretreatment of turbulent flow chromatography solid-phase extraction, the impurities removal and analytes concentration were automatically processed, and the lignans were separated rapidly and well. Seven lignans of Magnoliae Flos including epieudesmin, magnolin, 1-irioresinol-B-dimethyl ether, epi-magnolin, fargesin aschantin, and demethoxyaschantin were identified by comparing their retention behavior, UV spectra, and mass spectra with those of reference substances or literature data. The developed method was validated, and the good results showed that the method was not only automatic and rapid, but also accurate and reliable. The turbulent flow chromatography with online solid-phase extraction and high-performance liquid chromatography with tandem mass spectrometry method holds a high potential to become an effective method for the quality control of lignans in Magnoliae Flos and a useful tool for the analysis of other complex mixtures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Quantitative analysis of multiple fatty acid ethanolamides using ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Lin, Lin; Yang, Haifeng; Jones, Peter J H

    2012-12-01

    Fatty acid ethanolamides (FAE) represent a group of lipid signaling molecules associated with many physiological and pharmacological actions; however, low FAE tissue levels pose challenges in terms of analytical characterization. The objective was to develop a competent ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method for analysis of multiple FAE in animal and human tissue samples. Analytes were extracted using lipid-phase and solid-phase extraction procedures. Chromatographic separation was achieved using a gradient elution in 8 min. FAE were quantified by MS/MS in positive electrospray ionization mode. Linearity was shown in lower and higher FAE concentration ranges, with a limit of quantification (LOQ) ≤0.2 ng/ml for FAE including alpha-linolenoylethanolamide (ALEA), arachidonoylethanolamide (AEA), docosahexaenoylethanolamide (DHEA), linoleoylethanolamide (LEA), oleoylethanolamide (OEA) and palmitoylethanolamide (PEA). Accuracy was shown to be between 92.4% and 108.8%, and precision was <10% for all FAE species. In sum, this sensitive and reproducible method can be used to simultaneously determine multiple FAE at low concentrations in order to facilitate further study of the role of FAE on physiological state. Copyright © 2012 Elsevier Ltd. All rights reserved.

  10. Characterization of polyoxyethylene tallow amine surfactants in technical mixtures and glyphosate formulations using ultra-high performance liquid chromatography and triple quadrupole mass spectrometry

    USGS Publications Warehouse

    Tush, Daniel; Loftin, Keith A.; Meyer, Michael T.

    2013-01-01

    Little is known about the occurrence, fate, and effects of the ancillary additives in pesticide formulations. Polyoxyethylene tallow amine (POEA) is a non-ionic surfactant used in many glyphosate formulations, a widely applied herbicide both in agricultural and urban environments. POEA has not been previously well characterized, but has been shown to be toxic to various aquatic organisms. Characterization of technical mixtures using ultra-high performance liquid chromatography (UHPLC) and mass spectrometry shows POEA is a complex combination of homologs of different aliphatic moieties and ranges of ethoxylate units. Tandem mass spectrometry experiments indicate that POEA homologs generate no product ions readily suitable for quantitative analysis due to poor sensitivity. A comparison of multiple high performance liquid chromatography (HPLC) and UHPLC analytical columns indicates that the stationary phase is more important in column selection than other parameters for the separation of POEA. Analysis of several agricultural and household glyphosate formulations confirms that POEA is a common ingredient but ethoxylate distributions among formulations vary.

  11. Analysis of perfluorinated chemicals in umbilical cord blood by ultra-high performance liquid chromatography/tandem mass spectrometry.

    PubMed

    Lien, Guang-Wen; Wen, Ting-Wen; Hsieh, Wu-Shiun; Wu, Kuen-Yuh; Chen, Chia-Yang; Chen, Pau-Chung

    2011-03-15

    Perfluorinated compounds (PFCs) can cross the placental barrier and enter fetal circulation. This study aimed at developing a fast and sensitive ultra-high performance liquid chromatography/tandem mass spectrometry method for the determination of twelve perfluorinated compounds in cord blood. Samples were processed with protein precipitation using formic acid and methanol, mixed with stable isotope labeled standard, followed by sonication and centrifugation, and were analyzed using a Waters ACQUITY UPLC coupled with a Waters Quattro Premier XE triple-quadrupole mass spectrometer. The instrument was operated in selected reaction monitoring (SRM) with negative electrospray ionization. Using BEH C(18) column (2.1 mm×50 mm, 1.7 μm) with 10-mM N-methylmorpholine/methanol gradient elution provided a fast chromatographic separation (5.5 min) and sharp peaks. Intra- and inter-day calibration bias was less than 7% and intra- and inter-day calibration of relative standard deviations were within 0.02-8.22% for all the analytes and concentrations. The recoveries of PFCs spiked into bovine serum ranged from 85 to 104% with relative standard deviations from 0.02 to 6.37%. The limits of quantitation (LOQs), defined as a signal-to-noise ratio of ten, ranged from 0.15 to 3.1 ng/mL for the twelve PFCs. Perfluorooctanoic acid (PFOA), perfluorooctyl sulfonate (PFOS), perfluoroundecanoic acid (PFUA) and perfluorononanoic acid (PFNA) were detected in up to 68% of umbilical cord plasma (n=444) in Taiwan Birth Panel Study and the health effect of these chemicals on children developmental deserves further investigation. Copyright © 2011 Elsevier B.V. All rights reserved.

  12. Synthesis of monodisperse silica microspheres and modification with diazoresin for mixed-mode ultra high performance liquid chromatography separations.

    PubMed

    Cong, Hailin; Yu, Bing; Tian, Chao; Zhang, Shuai; Yuan, Hua

    2017-11-01

    Monodisperse silica particles with average diameters of 1.9-2.9 μm were synthesized by a modified Stöber method, in which tetraethyl orthosilicate was continuously supplied to the reaction mixture containing KCl electrolyte, water, ethanol, and ammonia. The obtained silica particles were modified by self-assembly with positively charged photosensitive diazoresin on the surface. After treatment with ultraviolet light, the ionic bonding between silica and diazoresin was converted into covalent bonding through a unique photochemistry reaction of diazoresin. Depending on the chemical structure of diazoresin and mobile phase composition, the diazoresin-modified silica stationary phase showed different separation mechanisms, including reversed phase and hydrophilic interactions. Therefore, a variety of baseline separation of benzene analogues and organic acids was achieved by using the diazoresin-modified silica particles as packing materials in ultra high performance liquid chromatography. According to the π-π interactional difference between carbon rings of fullerenes and benzene rings of diazoresin, C 60 and C 70 were also well separated by ultra-high performance liquid chromatography. Because it has a small size, the ∼2.5 μm monodisperse diazoresin-modified silica stationary phase shows ultra-high efficiency compared with the commercial C 18 -silica high-performance liquid chromatography stationary phase with average diameters of ∼5 μm. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Magnetic molecularly imprinted polymers for the determination of β-agonist residues in milk by ultra high performance liquid chromatography with tandem mass spectrometry.

    PubMed

    Liu, Hongcheng; Lin, Xin; Lin, Tao; Zhang, Yulong; Luo, Yinglan; Li, Qiwan

    2016-09-01

    A simple, accurate, and highly sensitive analytical method was developed in this study for the determination of nine β-agonists in milk. In this method, a new magnetic adsorbent of molecularly imprinted polymers/magnetic nanoparticles prepared by simple physical blending was adopted, which enabled magnetic solid-phase extraction. Thus, the resultant material can be separated from the solvent rapidly and conveniently by a magnet. Two kinds of molecularly imprinted polymer/magnetic nanoparticles materials were fabricated, and the characteristics of materials such as the ratio, pH, amount, desorption, and regeneration were investigated. The analytes were quantified by ultra high performance liquid chromatography coupled to an electrospray ionization tandem mass spectrometer operating in multiple reaction monitoring modes. The detection limit of the method was 0.003-0.3 μg/L, and the detection capability was 0.01-0.3 μg/L. The recoveries of these compounds were 65.7-114% at three spiked levels. Reproducibility represented by relative standard deviation was 11.2% or less. The method was successfully applied to the screening of real samples obtained from local markets and confirmation of the suspected target analytes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Ultra-high-performance liquid chromatography-tandem mass spectrometry measurement of climbazole deposition from hair care products onto artificial skin and human scalp.

    PubMed

    Chen, Guoqiang; Hoptroff, Michael; Fei, Xiaoqing; Su, Ya; Janssen, Hans-Gerd

    2013-11-22

    A sensitive and specific ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed and validated for the measurement of climbazole deposition from hair care products onto artificial skin and human scalp. Deuterated climbazole was used as the internal standard. Atmospheric pressure chemical ionization (APCI) in positive mode was applied for the detection of climbazole. For quantification, multiple reaction monitoring (MRM) transition 293.0>69.0 was monitored for climbazole, and MRM transition 296.0>225.1 for the deuterated climbazole. The linear range ran from 4 to 2000 ng mL(-1). The limit of detection (LOD) and the limit of quantification (LOQ) were 1 ng mL(-1) and 4 ng mL(-1), respectively, which enabled quantification of climbazole on artificial skin and human scalp at ppb level (corresponding to 16 ng cm(-2)). For the sampling of climbazole from human scalp the buffer scrub method using a surfactant-modified phosphate buffered saline (PBS) solution was selected based on a performance comparison of tape stripping, the buffer scrub method and solvent extraction in in vitro studies. Using this method, climbazole deposition in in vitro and in vivo studies was successfully quantified. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Ultra-high-performance liquid chromatography/tandem high-resolution mass spectrometry analysis of sixteen red beverages containing carminic acid: identification of degradation products by using principal component analysis/discriminant analysis.

    PubMed

    Gosetti, Fabio; Chiuminatto, Ugo; Mazzucco, Eleonora; Mastroianni, Rita; Marengo, Emilio

    2015-01-15

    The study investigates the sunlight photodegradation process of carminic acid, a natural red colourant used in beverages. For this purpose, both carminic acid aqueous standard solutions and sixteen different commercial beverages, ten containing carminic acid and six containing E120 dye, were subjected to photoirradiation. The results show different patterns of degradation, not only between the standard solutions and the beverages, but also from beverage to beverage. Due to the different beverage recipes, unpredictable reactions take place between the dye and the other ingredients. To identify the dye degradation products in a very complex scenario, a methodology was used, based on the combined use of principal component analysis with discriminant analysis and ultra-high-performance liquid chromatography coupled with tandem high resolution mass spectrometry. The methodology is unaffected by beverage composition and allows the degradation products of carminic acid dye to be identified for each beverage. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Purification and identification of corn peptides that facilitate alcohol metabolism by semi-preparative high-performance liquid chromatography and nano liquid chromatography with electrospray ionization tandem mass spectrometry.

    PubMed

    Ma, Zhi-Li; Hou, Tao; Shi, Wen; Liu, Wei-Wei; Ibrahim, Salam A; He, Hui

    2016-11-01

    In this study, peptides that facilitate alcohol metabolism were purified and identified from corn protein hydrolysates. The ultra-filtered fraction with a molecular weight < 3 kDa (F3) potential activity was separated into six fractions (F3-H1-F3-H6) by semi-preparative high-performance liquid chromatography. Among the resultant six fractions, F3-H4 and F3-H5 exhibited the highest ability to eliminate alcohol in vivo. A total of 16 peptides with strong signal values were identified from F3-H4 and F3-H5 fractions by nano liquid chromatography coupled with electrospray ionization tandem mass spectrometry. Several identified peptides were then selected and synthesized to determine their potential to facilitate alcohol metabolism. We found that Leu-Leu and Pro-Phe were the key structure units in Gln-Leu-Leu-Pro-Phe responsible for this peptide's ability to facilitate alcohol metabolism. However, the role of Leu-Leu and Pro-Phe may be affected by peptide chain length and hydrophobic properties. Our results have thus provided some insight into the study of the structure-activity relationships of corn peptides. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. [Determination of di (hydrogenated tallow alkyl) dimethyl ammonium compounds in textile auxiliaries by ultra-high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Zhu, Feng

    2015-01-01

    A method has been developed for the determination of di (hydrogenated tallow alkyl) dimethyl ammonium compounds (DHTDMAC) in textile auxiliaries by ultra-high performance liquid chromatography-tandem mass spectrometry. (UPLC-MS/MS). The samples were extracted and diluted with acidified methanol by 5% (v/v) formic acid under ultrasonic assistance. The separation was performed on an Eclipse Plus C18 column (50 mm x 2.1 mm, 1.8 microm) using 0.1% (v/v) formic acid solution and methanol as the mobile phases. Identification and quantification were achieved by UPLC-MS/MS with electrospray ionization (ESI) source in positive ion mode and multiple reaction monitoring (MRM) mode. The results indicated that the calibration curve of DHTDMAC showed good linear relationship between peak area and mass concentration in the range of 10-280 microg/L with the correlation coefficient (r2) of 0.9991. The limit of detection (LOD, S/N=3) and the limit of quantification (LOQ, S/N= 10) of this method were 3 mg/kg and 10 mg/kg, respectively. The average recoveries from three typical textile auxiliary matrices including dispersant, antistatic agent and fabric softener, at three spiked levels were in the range of 97.2%-108.3% with the relative standard deviations (RSDs) of 1.5%-4.6%. The method is sensitive, accurate, simple and effective for the analysis of DHTDMAC in textile auxiliaries.

  18. A novel high-throughput method for supported liquid extraction of retinol and alpha-tocopherol from human serum and simultaneous quantitation by liquid chromatography tandem mass spectrometry.

    PubMed

    Hinchliffe, Edward; Rudge, James; Reed, Paul

    2016-07-01

    Measurement of vitamin A (retinol) and E (alpha-tocopherol) in UK clinical laboratories is currently performed exclusively by high-performance liquid chromatography with ultraviolet detection. We investigated whether retinol and alpha-tocopherol could be measured simultaneously by liquid chromatography tandem mass spectrometry. Serum samples (100 μL) were extracted using Isolute + Supported Liquid Extraction plates. Chromatography was performed on a Phenomenex Kinetex Biphenyl 2.6 μm, 50 × 2.1 mm column, and liquid chromatography tandem mass spectrometry on a Waters Acquity TQD. Injection-to-injection time was 4.3 min. The assay was validated according to published guidelines. Patient samples were used to compare liquid chromatography tandem mass spectrometry and high-performance liquid chromatography with ultraviolet detection methods. For retinol and alpha-tocopherol, respectively, the assay was linear up to 6.0 and 80.0 μmol/L, and lower limit of quantification was 0.07 and 0.26 μmol/L. Intra and interassay imprecision were within desirable analytical specifications. Analysis of quality control material aligned to NIST SRM 968e, and relative spiked recovery from human serum, both yielded results within 15% of target values. Method comparison with high-performance liquid chromatography with ultraviolet detection methodology demonstrated a negative bias for retinol and alpha-tocopherol by the liquid chromatography tandem mass spectrometry method. Analysis of United Kingdom National External Quality Assurance Scheme samples yielded mean bias from the target value of +3.0% for retinol and -11.2% for alpha-tocopherol. We have developed a novel, high-throughput method for extraction of retinol and alpha-tocopherol from human serum followed by simultaneous quantitation by liquid chromatography tandem mass spectrometry. The method offers a rapid, sensitive, specific and cost-effective alternative to high-performance liquid chromatography with

  19. Measurement of serum 3-epi-25-hydroxyvitamin D3, 25-hydroxyvitamin D3 and 25-hydroxyvitamin D2 in infant, paediatric and adolescent populations of Korea using ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Cho, Sung E; Kim, Sollip; Kim, Young D; Lee, Hyojung; Seo, Dong H; Song, Junghan; Um, Tae H; Cho, Chong R; Kim, Nam H; Hwang, Jong H

    2017-09-01

    Background We evaluated the performance of ultra-performance liquid chromatography-tandem mass spectrometry to measure serum 3-epi-25-hydroxyvitamin D 3 , 25-hydroxyvitamin D 3 and 25-hydroxyvitamin D 2 concentrations in 519 infant, paediatric and adolescent serum samples in Korea. Methods We used a Kinetex XB-C18 column and isocratic methanol/water (77.5/22.5, v/v) with 0.025% (v/v) high-performance liquid chromatography solvent additive flowing at 0.25 mL/min, yielding an 11 min/sample run time. A TQD triple quadrupole mass spectrometer in electrospray ionization positive ion mode with multiple reaction monitoring transition via an MSMS vitamin D kit was used to evaluate precision, carryover, ion suppression and linearity. Samples were prepared using the 4-phenyl-1,2,4-triazoline-3,5-dione derivatization method. Results Intra- and inter-run precisions were 1.23-13.28% and 1.02-10.08%, respectively. Group carryovers were -0.27% and 0.10%, respectively. There was no ion suppression. The calibration curve showed good linearity from calibrator Level 1 (11.75 nmol/L) to 6 (375 nmol/L) with R 2  > 0.9999. The 3-epi-25-hydroxyvitamin D 3 and 25-hydroxyvitamin D 3 peaks were clearly separated in the extracted ion chromatogram. Infant serum samples 3-epi-25-hydroxyvitamin D 3 concentrations were significantly higher than paediatric and adolescent concentrations. Conclusions The ultra-performance liquid chromatography-tandem mass spectrometry assay performed acceptably, clearly separating 3-epi-25-hydroxyvitamin D 3 from 25-hydroxyvitamin D 3 . High 3-epi-25-hydroxyvitamin D 3 concentrations were observed in infant but not in paediatric and adolescent serum samples.

  20. Direct large volume injection ultra-high performance liquid chromatography-tandem mass spectrometry determination of artificial sweeteners sucralose and acesulfame in well water.

    PubMed

    Wu, Minghuo; Qian, Yichao; Boyd, Jessica M; Hrudey, Steve E; Le, X Chris; Li, Xing-Fang

    2014-09-12

    Acesulfame (ACE) and sucralose (SUC) have become recognized as ideal domestic wastewater contamination indicators. Liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) analysis is commonly used; however, the sensitivity of SUC is more than two orders of magnitude lower than that of ACE, limiting the routine monitoring of SUC. To address this issue, we examined the ESI behavior of both ACE and SUC under various conditions. ACE is ionic in aqueous solution and efficiently produces simple [M-H](-) ions, but SUC produces multiple adduct ions, limiting its sensitivity. The formic acid (FA) adducts of SUC [M+HCOO](-) are sensitively and reproducibly generated under the LC-MS conditions. When [M+HCOO](-) is used as the precursor ion for SUC detection, the sensitivity increases approximately 20-fold compared to when [M-H](-) is the precursor ion. To further improve the limit of detection (LOD), we integrated the large volume injection approach (500μL injection) with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), which reduced the method detection limit (MDL) to 0.2ng/L for ACE and 5ng/L for SUC. To demonstrate the applicability of this method, we analyzed 100 well water samples collected in Alberta. ACE was detected in 24 wells at concentrations of 1-1534ng/L and SUC in 8 wells at concentrations of 65-541ng/L. These results suggest that wastewater is the most likely source of ACE and SUC impacts in these wells, suggesting the need for monitoring the quality of domestic well water. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Analysis of new psychoactive substances in human urine by ultra-high performance supercritical fluid and liquid chromatography: Validation and comparison.

    PubMed

    Borovcová, Lucie; Pauk, Volodymyr; Lemr, Karel

    2018-05-01

    New psychoactive substances represent serious social and health problem as tens of new compounds are detected in Europe annually. They often show structural proximity or even isomerism, which complicates their analysis. Two methods based on ultra high performance supercritical fluid chromatography and ultra high performance liquid chromatography with mass spectrometric detection were validated and compared. A simple dilute-filter-and-shoot protocol utilizing propan-2-ol or methanol for supercritical fluid or liquid chromatography, respectively, was proposed to detect and quantify 15 cathinones and phenethylamines in human urine. Both methods offered fast separation (<3 min) and short total analysis time. Precision was well <15% with a few exceptions in liquid chromatography. Limits of detection in urine ranged from 0.01 to 2.3 ng/mL, except for cathinone (5 ng/mL) in supercritical fluid chromatography. Nevertheless, this technique distinguished all analytes including four pairs of isomers, while liquid chromatography was unable to resolve fluoromethcathinone regioisomers. Concerning matrix effects and recoveries, supercritical fluid chromatography produced more uniform results for different compounds and at different concentration levels. This work demonstrates the performance and reliability of supercritical fluid chromatography and corroborates its applicability as an alternative tool for analysis of new psychoactive substances in biological matrixes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Bile acid profiling and quantification in biofluids using ultra-performance liquid chromatography tandem mass spectrometry.

    PubMed

    Sarafian, Magali H; Lewis, Matthew R; Pechlivanis, Alexandros; Ralphs, Simon; McPhail, Mark J W; Patel, Vishal C; Dumas, Marc-Emmanuel; Holmes, Elaine; Nicholson, Jeremy K

    2015-10-06

    Bile acids are important end products of cholesterol metabolism. While they have been identified as key factors in lipid emulsification and absorption due to their detergent properties, bile acids have also been shown to act as signaling molecules and intermediates between the host and the gut microbiota. To further the investigation of bile acid functions in humans, an advanced platform for high throughput analysis is essential. Herein, we describe the development and application of a 15 min UPLC procedure for the separation of bile acid species from human biofluid samples requiring minimal sample preparation. High resolution time-of-flight mass spectrometry was applied for profiling applications, elucidating rich bile acid profiles in both normal and disease state plasma. In parallel, a second mode of detection was developed utilizing tandem mass spectrometry for sensitive and quantitative targeted analysis of 145 bile acid (BA) species including primary, secondary, and tertiary bile acids. The latter system was validated by testing the linearity (lower limit of quantification, LLOQ, 0.25-10 nM and upper limit of quantification, ULOQ, 2.5-5 μM), precision (≈6.5%), and accuracy (81.2-118.9%) on inter- and intraday analysis achieving good recovery of bile acids (serum/plasma 88% and urine 93%). The ultra performance liquid chromatography-mass spectrometry (UPLC-MS)/MS targeted method was successfully applied to plasma, serum, and urine samples in order to compare the bile acid pool compositional difference between preprandial and postprandial states, demonstrating the utility of such analysis on human biofluids.

  3. [Determination of 11 industrial antioxidants in the aqueous simulants by ultra-performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Fan, Sai; Zou, Jianhong; Li, Liping; Zhang, Nan; Liu, Wei; Li, Bing; Zhao, Xudong; Wu, Guohua; Xue, Ying; Zhao, Rong

    2014-09-01

    An ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method has been developed to identify and determine 11 industrial antioxidants in the aqueous simulants. A ProElut PLS SPE column was used for the enrichment, and an ACQUITY UPLC BEH C18 UPLC column (100 mm x 2.1 mm, 1.7 μm) was used for separation by the gradient elution with pure water and acetonitrile as the mobile phases. The MS/MS detection was performed with an electrospray ionization (ESI) source in negative mode. The external standard method was used for quantitation in the present study. The linear ranges of the 11 analytes were from 5.0 to 100 μg/L. The coefficients of correlation were greater than 0.995. The recoveries of blank aqueous simulants fortified with the 11 analytes at the levels of 5.0, 10.0 and 20.0 μg/L were 61.4% to 109.4% with the relative standard deviations varied from 3.9% to 18.2% (n = 6). The LODs and LOQs of the 11 analytes in aqueous simulants were 0.2-1.0 μg/L and 0.5-3.0 μg/L, respectively. This method is highly sensitive and accurate, and can be applied to the determination of the 11 trace industrial antioxidants in the aqueous simulants.

  4. Simultaneous and rapid determination of deoxynivalenol and its acetylate derivatives in wheat flour and rice by ultra high performance liquid chromatography with photo diode array detection.

    PubMed

    Xu, Jiao-Jiao; Zhou, Jian; Huang, Bai-Fen; Cai, Zeng-Xuan; Xu, Xiao-Min; Ren, Yi-Ping

    2016-06-01

    A simple and reliable method of ultra high performance liquid chromatography coupled with photo-diode array detection has been proposed for the simultaneous determination of deoxynivalenol and its acetylated derivatives in wheat flour and rice, especially focusing on the optimization of sample extraction, cleanup, and chromatographic separation conditions. Sample pretreatment consisted of a first step using a quick, easy, cheap, effective, rugged, and safe based extraction procedure and a subsequent cleanup step based on solid-phase extraction. The method was extensively validated in wheat flour and rice, obtaining satisfactory analytical performance with good linearity (R(2) ≥ 0.999), acceptable recoveries (80.0-104.4%), and repeatability (RSDs 1.3-10.7%). The limits of detection (21.7-57.4 μg/kg) and quantitation (72.3-191.4 μg/kg) for deoxynivalenols were lower than those usually permitted by various countries' legislation in these food matrices. The method was applied to 34 wheat and rice samples. The results were further compared with results of ultra high performance liquid chromatography with electrospray ionization tandem mass spectrometry. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Simultaneous identification and quantification of bisphenol A and 12 bisphenol analogues in environmental samples using precolumn derivatization and ultra high performance liquid chromatography with tandem mass spectrometry.

    PubMed

    Wang, Zhonghe; Yu, Jing; Yao, Jiaxi; Wu, Linlin; Xiao, Hang; Wang, Jun; Gao, Rong

    2018-02-10

    A method for the identification and quantification of bisphenol A and 12 bisphenol analogues in river water and sediment samples combining liquid-liquid extraction, precolumn derivatization, and ultra high-performance liquid chromatography coupled with tandem mass spectrometry was developed and validated. Analytes were extracted from the river water sample using a liquid-liquid extraction method. Dansyl chloride was selected as a derivatization reagent. Derivatization reaction conditions affecting production of the dansyl derivatives were tested and optimized. All the derivatized target compounds were well separated and eluted in 10 min. Dansyl chloride labeled compounds were analyzed using a high-resolution mass spectrometer with electrospray ionization in the positive mode, and the results were confirmed and quantified in the parallel reaction monitoring mode. The method validation results showed a satisfactory level of sensitivity. Linearity was assessed using matrix-matched standard calibration, and good correlation coefficients were obtained. The limits of quantification for the analytes ranged from 0.005 to 0.02 ng/mL in river water and from 0.15 to 0.80 ng/g in sediment. Good reproducibility of the method in terms of intra- and interday precision was achieved, yielding relative standard deviations of less than 10.1 and 11.6%, respectively. Finally, this method was successfully applied to the analysis of real samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. High-throughput and simultaneous analysis of eight central-acting muscle relaxants in human plasma by ultra-performance liquid chromatography-tandem mass spectrometry in the positive and negative ionization modes.

    PubMed

    Ogawa, Tadashi; Hattori, Hideki; Kaneko, Rina; Ito, Kenjiro; Iwai, Masae; Mizutani, Yoko; Arinobu, Tetsuya; Ishii, Akira; Seno, Hiroshi

    2011-06-01

    In this report, a high-throughput and sensitive method for analysis of eight central-acting muscle relaxants in human plasma by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) in the positive and negative ionization modes using tolbutamide as internal standard is presented. After pretreatment of a plasma sample by solid-phase extraction with an Oasis HLB cartridge, muscle relaxants were analyzed by UPLC with Acquity UPLC BEH C(18) column and Acquity TQD tandem quadrupole mass spectrometer equipped with an electrospray ionization interface. The calibration curves for muscle relaxants spiked into human plasma equally showed good linearities in the nanogram per milliliter order range. The detection limits (signal-to-noise ratio = 3) was as low as 0.1-2 ng/mL. The method gave satisfactory recovery rates, accuracy, and precision for quality control samples spiked with muscle relaxants. To further validate the present method, 250 mg of chlorphenesin carbamate was orally administered to a healthy male volunteer, and the concentrations of chlorphenesin carbamate in plasma were measured 0.5, 1, 2, 4, 6, and 8 h after dosing; their concentrations in human plasma were between 0.62 and 2.44 μg/mL. To our knowledge, this is the first report describing simultaneous analysis of over more than two central-acting muscle relaxants by liquid chromatography-tandem mass spectrometry. This has been realized by the capability of our instrument for simultaneous multiple reaction monitoring of the target compounds in both positive and negative ionization modes. Therefore, the present method seems very useful in forensic and clinical toxicology and pharmacokinetic studies.

  7. Hydrophilic interaction ultra-performance liquid chromatography coupled with triple-quadrupole tandem mass spectrometry for highly rapid and sensitive analysis of underivatized amino acids in functional foods.

    PubMed

    Zhou, Guisheng; Pang, Hanqing; Tang, Yuping; Yao, Xin; Mo, Xuan; Zhu, Shaoqing; Guo, Sheng; Qian, Dawei; Qian, Yefei; Su, Shulan; Zhang, Li; Jin, Chun; Qin, Yong; Duan, Jin-ao

    2013-05-01

    This work presented a new analytical methodology based on hydrophilic interaction ultra-performance liquid chromatography coupled with triple-quadrupole tandem mass spectrometry in multiple-reaction monitoring mode for analysis of 24 underivatized free amino acids (FAAs) in functional foods. The proposed method was first reported and validated by assessing the matrix effects, linearity, limit of detections and limit of quantifications, precision, repeatability, stability and recovery of all target compounds, and it was used to determine the nutritional substances of FAAs in ginkgo seeds and further elucidate the nutritional value of this functional food. The result showed that ginkgo seed turned out to be a good source of FAAs with high levels of several essential FAAs and to have a good nutritional value. Furthermore, the principal component analysis was performed to classify the ginkgo seed samples on the basis of 24 FAAs. As a result, the samples could be mainly clustered into three groups, which were similar to areas classification. Overall, the presented method would be useful for the investigation of amino acids in edible plants and agricultural products.

  8. Ultra-high-pressure liquid chromatography-tandem mass spectrometry for the analysis of six resorcylic acid lactones in bovine milk.

    PubMed

    Xia, Xi; Li, Xiaowei; Ding, Shuangyang; Zhang, Suxia; Jiang, Haiyang; Li, Jiancheng; Shen, Jianzhong

    2009-03-20

    This work reports a rapid, reliable and sensitive multi-residue method for the simultaneous determination of six resorcylic acid lactones in bovine milk by ultra-high-pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The resorcylic acid lactones were extracted, purified, and concentrated from milk samples in one step using a solid-phase extraction (SPE) cartridge that contained a polymeric mixed-mode anion-exchange sorbent. The analysis was performed on a Waters Acquity BEH C(18) column utilizing a gradient elution profile. Each LC run was completed in 3.5 min. The analytes were detected by multiple reaction monitoring (MRM) using electrospray ionization (ESI) negative mode. Mean recoveries from fortified samples ranged from 92.6% to 112.5%, with relative standard deviations lower than 11.4%. Using 5 mL bovine milk, the limits of detection and quantification for resorcylic acid lactones were in the ranges of 0.01-0.05 and 0.05-0.2 microg/L, respectively. The application of this newly developed method was demonstrated by analyzing bovine milk samples from markets.

  9. An ultra-high pressure liquid chromatography-tandem mass spectrometry method for the quantification of teicoplanin in plasma of neonates.

    PubMed

    Begou, O; Kontou, A; Raikos, N; Sarafidis, K; Roilides, E; Papadoyannis, I N; Gika, H G

    2017-03-15

    The development and validation of an ultra-high pressure liquid chromatography (UHPLC) tandem mass spectrometry (MS/MS) method was performed with the aim to be applied for the quantification of plasma teicoplanin concentrations in neonates. Pharmacokinetic data of teicoplanin in the neonatal population is very limited, therefore, a sensitive and reliable method for the determination of all isoforms of teicoplanin applied in a low volume of sample is of real importance. Teicoplanin main components were extracted by a simple acetonitrile precipitation step and analysed on a C18 chromatographic column by a triple quadrupole MS with electrospray ionization. The method provides quantitative data over a linear range of 25-6400ng/mL with LOD 8.5ng/mL and LOQ 25ng/mL for total teicoplanin. The method was applied in plasma samples from neonates to support pharmacokinetic data and proved to be a reliable and fast method for the quantification of teicoplanin concentration levels in plasma of infants during therapy in Intensive Care Unit. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Determination of biocides in different environmental matrices by use of ultra-high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Chen, Zhi-Feng; Ying, Guang-Guo; Lai, Hua-Jie; Chen, Feng; Su, Hao-Chang; Liu, You-Sheng; Peng, Fu-Qiang; Zhao, Jian-Liang

    2012-12-01

    A sensitive and robust method using solid-phase extraction and ultrasonic extraction for preconcentration followed by ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS-MS) has been developed for determination of 19 biocides: eight azole fungicides (climbazole, clotrimazole, ketoconazole, miconazole, fluconazole, itraconazole, thiabendazole, and carbendazim), two insect repellents (N,N-diethyl-3-methylbenzamide (DEET), and icaridin (also known as picaridin)), three isothiazolinone antifouling agents (1,2-benzisothiazolinone (BIT), 2-n-octyl-4-isothiazolinone (OIT), and 4,5-dichloro-2-n-octyl-isothiazolinone (DCOIT)), four paraben preservatives (methylparaben, ethylparaben, propylparaben, and butylparaben), and two disinfectants (triclosan and triclocarban) in surface water, wastewater, sediment, sludge, and soil. Recovery of the target compounds from surface water, influent, effluent, sediment, sludge, and soil was mostly in the range 70-120%, with corresponding method quantification limits ranging from 0.01 to 0.31 ng L(-1), 0.07 to 7.48 ng L(-1), 0.01 to 3.90 ng L(-1), 0.01 to 0.45 ng g(-1), 0.01 to 6.37 ng g(-1), and 0.01 to 0.73 ng g(-1), respectively. Carbendazim, climbazole, clotrimazole, methylparaben, miconazole, triclocarban, and triclosan were detected at low ng L(-1) (or ng g(-1)) levels in surface water, sediment, and sludge-amended soil. Fifteen target compounds were found in influent samples, at concentrations ranging between 0.4 (thiabendazole) and 372 ng L(-1) (methylparaben). Fifteen target compounds were found in effluent samples, at concentrations ranging between 0.4 (thiabendazole) and 114 ng L(-1) (carbendazim). Ten target compounds were found in dewatered sludge samples, at concentrations ranging between 1.1 (DEET) and 887 ng g(-1) (triclocarban).

  11. Quantification of cefazolin in serum and adipose tissue by ultra high performance liquid chromatography-Tandem mass spectrometry (UHPLC-MS/MS): application to a pilot study of obese women undergoing cesarean delivery.

    PubMed

    Lillico, Ryan; Sayre, Casey L; Sitar, Daniel S; Davies, Neal M; Baron, Cynthia M; Lakowski, Ted M

    2016-09-15

    Higher doses of cefazolin are required in obese patients for preoperative antibiotic prophylaxis, owing to its low lipophilicity. An ultra high performance liquid chromatography-tandem mass spectrometry method was developed to quantify cefazolin in serum and adipose tissue from 6 obese patients undergoing cesarean delivery, and using stable-isotope labeled cefazolin as an internal standard. The method has a 2μg/g lower limit of quantitation. The concentration in adipose tissue was 3.4±1.6μg/mL, which is less than half of the reported minimum inhibitory concentration of 8μg/mL for cefazolin. Serum cefazolin concentrations were more than 30-fold higher than in adipose tissue. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. An isotope dilution ultra high performance liquid chromatography-tandem mass spectrometry method for the simultaneous determination of sugars and humectants in tobacco products.

    PubMed

    Wang, Liqun; Cardenas, Roberto Bravo; Watson, Clifford

    2017-09-08

    CDC's Division of Laboratory Sciences developed and validated a new method for the simultaneous detection and measurement of 11 sugars, alditols and humectants in tobacco products. The method uses isotope dilution ultra high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) and has demonstrated high sensitivity, selectivity, throughput and accuracy, with recoveries ranging from 90% to 113%, limits of detection ranging from 0.0002 to 0.0045μg/mL and coefficients of variation (CV%) ranging from 1.4 to 14%. Calibration curves for all analytes were linear with linearity R 2 values greater than 0.995. Quantification of tobacco components is necessary to characterize tobacco product components and their potential effects on consumer appeal, smoke chemistry and toxicology, and to potentially help distinguish tobacco product categories. The researchers analyzed a variety of tobacco products (e.g., cigarettes, little cigars, cigarillos) using the new method and documented differences in the abundance of selected analytes among product categories. Specifically, differences were detected in levels of selected sugars found in little cigars and cigarettes, which could help address appeal potential and have utility when product category is unknown, unclear, or miscategorized. Copyright © 2017. Published by Elsevier B.V.

  13. Ultra high performance liquid chromatography tandem mass spectrometry for rapid analysis of trace organic contaminants in water

    PubMed Central

    2013-01-01

    Background The widespread utilization of organic compounds in modern society and their dispersion through wastewater have resulted in extensive contamination of source and drinking waters. The vast majority of these compounds are not regulated in wastewater outfalls or in drinking water while trace amounts of certain compounds can impact aquatic wildlife. Hence it is prudent to monitor these contaminants in water sources until sufficient toxicological data relevant to humans becomes available. A method was developed for the analysis of 36 trace organic contaminants (TOrCs) including pharmaceuticals, pesticides, steroid hormones (androgens, progestins, and glucocorticoids), personal care products and polyfluorinated compounds (PFCs) using a single solid phase extraction (SPE) technique with ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The method was applied to a variety of water matrices to demonstrate method performance and reliability. Results UHPLC-MS/MS in both positive and negative electrospray ionization (ESI) modes was employed to achieve optimum sensitivity while reducing sample analysis time (<20 min) compared with previously published methods. The detection limits for most compounds was lower than 1.0 picogram on the column while reporting limits in water ranged from 0.1 to 15 ng/L based on the extraction of a 1 L sample and concentration to 1 mL. Recoveries in ultrapure water for most compounds were between 90-110%, while recoveries in surface water and wastewater were in the range of 39-121% and 38-141% respectively. The analytical method was successfully applied to analyze samples across several different water matrices including wastewater, groundwater, surface water and drinking water at different stages of the treatment. Among several compounds detected in wastewater, sucralose and TCPP showed the highest concentrations. Conclusion The proposed method is sensitive, rapid and robust; hence it can

  14. Analysis of food polyphenols by ultra high-performance liquid chromatography coupled to mass spectrometry: an overview.

    PubMed

    Motilva, Maria-José; Serra, Aida; Macià, Alba

    2013-05-31

    Phenolic compounds, which are widely distributed in plant-derived foods, recently attracted much attention due to their health benefits, so their determination in food samples is a topic of increasing interest. In the last few years, the development of chromatographic columns packed with sub-2μm particles and the modern high resolution mass spectrometry (MS) have opened up new possibilities for improving the analytical methods for complex sample matrices, such as ingredients, foods and biological samples. In addition, they have emerged as an ideal tool for profiling complex samples due to its speed, efficiency, sensitivity and selectivity. The present review addresses the use of the improved liquid chromatography (LC), ultra-high performance LC (UHPLC), coupled to MS or tandem MS (MS/MS) as the detector system for the determination of phenolic compounds in food samples. Additionally, the different strategies to extract, quantify the phenolic compounds and to reduce the matrix effect (%ME) are also reviewed. Finally, a briefly outline future trends of UHPLC-MS methods is commented. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Rapid detection of multiple class pharmaceuticals in both municipal wastewater and sludge with ultra high performance liquid chromatography tandem mass spectrometry.

    PubMed

    Yuan, Xiangjuan; Qiang, Zhimin; Ben, Weiwei; Zhu, Bing; Liu, Junxin

    2014-09-01

    This work described the development, optimization and validation of an analytical method for rapid detection of multiple-class pharmaceuticals in both municipal wastewater and sludge samples based on ultrasonic solvent extraction, solid-phase extraction, and ultra high performance liquid chromatography-tandem mass spectrometry quantification. The results indicated that the developed method could effectively extract all the target pharmaceuticals (25) in a single process and analyze them within 24min. The recoveries of the target pharmaceuticals were in the range of 69%-131% for wastewater and 54%-130% for sludge at different spiked concentration levels. The method quantification limits in wastewater and sludge ranged from 0.02 to 0.73ng/L and from 0.02 to 1.00μg/kg, respectively. Subsequently, this method was validated and applied for residual pharmaceutical analysis in a wastewater treatment plant located in Beijing, China. All the target pharmaceuticals were detected in the influent samples with concentrations varying from 0.09ng/L (tiamulin) to 15.24μg/L (caffeine); meanwhile, up to 23 pharmaceuticals were detected in sludge samples with concentrations varying from 60ng/kg (sulfamethizole) to 8.55mg/kg (ofloxacin). The developed method demonstrated its selectivity, sensitivity, and reliability for detecting multiple-class pharmaceuticals in complex matrices such as municipal wastewater and sludge. Copyright © 2014. Published by Elsevier B.V.

  16. Fast and comprehensive analysis of secondary metabolites in cocoa products using ultra high-performance liquid chromatography directly after pressurized liquid extraction.

    PubMed

    Damm, Irina; Enger, Eileen; Chrubasik-Hausmann, Sigrun; Schieber, Andreas; Zimmermann, Benno F

    2016-08-01

    Fast methods for the extraction and analysis of various secondary metabolites from cocoa products were developed and optimized regarding speed and separation efficiency. Extraction by pressurized liquid extraction is automated and the extracts are analyzed by rapid reversed-phase ultra high-performance liquid chromatography and normal-phase high-performance liquid chromatography methods. After extraction, no further sample treatment is required before chromatographic analysis. The analytes comprise monomeric and oligomeric flavanols, flavonols, methylxanthins, N-phenylpropenoyl amino acids, and phenolic acids. Polyphenols and N-phenylpropenoyl amino acids are separated in a single run of 33 min, procyanidins are analyzed by normal-phase high-performance liquid chromatography within 16 min, and methylxanthins require only 6 min total run time. A fourth method is suitable for phenolic acids, but only protocatechuic acid was found in relevant quantities. The optimized methods were validated and applied to 27 dark chocolates, one milk chocolate, two cocoa powders and two food supplements based on cocoa extract. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Ultra high performance liquid chromatography-tandem mass spectrometry vs. commercial immunoassay for determination of vancomycin plasma concentration in children. Possible implications for everyday clinical practice.

    PubMed

    Barco, Sebastiano; Castagnola, Elio; Gennai, Iulian; Barbagallo, Laura; Loy, Anna; Tripodi, Gino; Cangemi, Giuliana

    2016-10-01

    Vancomycin therapeutic drug monitoring (TDM) is necessary for effective and safetherapy. The aim of the this paper was to develop a specific and robust ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for vancomycin quantification starting from low plasma volumes to be applied for the routine TDM in children. Samples from children receiving intravenous vancomycin were analysed using a TSQ Quantum Access MAX Triple Quadrupole system coupled with an Accela 1250 UHPLC system after a rapid protein precipitation. Gradient separation chromatography was carried out using a Hypersil GOLD aQ C18 column (50 × 2.1 mm, particle size 1.9 μm). Method performance was validated following international guidelines. UHPLC-MS/MS allowed a rapid and specific quantification of vancomycin over the range 0.1-128 μg/mL from 50 μL of plasma with high reproducibility and accuracy in the absence of matrix effect. The comparison with the commercial immunoassay performed on 138 samples demonstrated the presence of a proportional bias. The concentrations of vancomycin measured with immunoassay were found to be 4.5% (95% CI: 1.3-7.7) higher than those determined with UHPLC-MS/MS. Importantly, a clinical discordance was found in about 10% of samples analysed. This new UHPLC-MS/MS method is accurate and specific for the measurement of vancomycin starting from small (50 μL) plasma volumes. The use of UHPLC-MS/MS is recommended to prevent a misclassification of therapeutic or toxic vancomycin levels in paediatrics.

  18. [Simultaneous determination of 11 bisphenols in plastic bottled drinking water by ultra performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Gou, Xinlei; Gao, Xia; Hu, Guanghui; Chi, Haitao; Le, Shengfeng; Wang, Wei; Liu, Weili

    2014-09-01

    A sensitive method was developed for the simultaneous determination of 11 bisphenols in plastic bottled drinking water by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The samples were freeze-dried under vacuum and then dissolved with methanol. The separation was performed on a UPLC BEH C18 column (100 mm x 2.1 mm, 1.7 μm) by using 0.1% (v/v) NH3 · H2O and methanol as mobile phases with gradient elution at a flow rate of 0.2 mL/min. The electrospray ionization (ESI) source in negative ion mode was used for the analysis of the 11 bisphenols in the multiple reaction monitoring (MRM) mode. The results verified that the standard curves for the 11 bisphenols were obtained with good correlation coefficients (R2) > 0.997 in their concentration ranges. The limits of detection (LOD, S/N = 3) for the 11 bisphenols were in the range of 0.01-1.00 μg/L. The mean recoveries for the 11 bisphenols at three spiked levels (low, middle, high) were 75.3%-102.1% with the relative standard deviations of 1.5%-8.9%. Seven plastic bottled drinking water samples were tested, and no bisphenol was found. The method is accurate, simple, rapid and feasible for the simultaneous determination of bisphenols in plastic bottled drinking water.

  19. Quantitative analysis of flavonoids, alkaloids and saponins of Banxia Xiexin decoction using ultra-high performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

    PubMed

    Wang, Ying; Xu, Ranchi; Xiao, Juan; Zhang, Jian; Wang, Xinhong; An, Rui; Ma, Yueming

    2014-01-01

    Banxia Xiexin decoction (BXD) is an effective Chinese Medicinal Prescription in treating gastroenteritis diseases. In this study an ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was developed to separate and determine 18 major active ingredients of BXD in order to guarantee quality. The separation of ten flavonoids, four alkaloids and four saponins was accomplished on an Acquity BEH C18 (2.1mm×100mm, 1.7μm) column using gradient elution with 0.1% (v/v) formic acid water (A) and 0.1% (v/v) formic acid in methanol (B). All the analytes were detected in positive electrospray ionization tandem mass spectrometry by selective reaction monitoring (SRM) mode. A good linear regression relationship for each analyte was obtained over the range from 2.41-438ng/ml to 20.75-4150ng/ml. The precision was evaluated by intra- and inter-day assays with relative standard deviation (RSD) less than 7.7%. The recovery measured at three concentration levels varied from 92.4% to 107.8%. The method sensitivity expressed as LOQ was typically 0.97-4.15ng/ml. The assay was successfully applied for determination of the 18 bioactive compounds in BXD. The results indicated that the new UPLC-MS/MS method was rapid and accurate, and could be reliably utilized as a quality control method for BXD. Copyright © 2013 Elsevier B.V. All rights reserved.

  20. Stable isotope dilution ultra-high performance liquid chromatography-tandem mass spectrometry quantitative profiling of tryptophan-related neuroactive substances in human serum and cerebrospinal fluid.

    PubMed

    Hényková, Eva; Vránová, Hana Přikrylová; Amakorová, Petra; Pospíšil, Tomáš; Žukauskaitė, Asta; Vlčková, Magdaléna; Urbánek, Lubor; Novák, Ondřej; Mareš, Jan; Kaňovský, Petr; Strnad, Miroslav

    2016-03-11

    Many compounds related to L-tryptophan (L-TRP) have interesting biological or pharmacological activity, and their abnormal neurotransmission seems to be linked to a wide range of neurodegenerative and psychiatric diseases. A high-throughput method based on ultra-high performance liquid chromatography connected to electrospray tandem mass spectrometry (UHPLC-ESI-MS/MS) was developed for the quantitative analysis of L-TRP and 16 of its metabolites in human serum and cerebrospinal fluid (CSF), representing both major and minor routes of L-TRP catabolism. The combination of a fast LC gradient with selective tandem mass spectrometry enabled accurate analysis of almost 100 samples in 24h. The standard isotope dilution method was used for quantitative determination. The method's lower limits of quantification for serum and cerebrospinal fluid ranged from 0.05 to 15nmol/L and 0.3 to 45nmol/L, respectively. Analytical recoveries ranged from 10.4 to 218.1% for serum and 22.1 to 370.0% for CSF. The method's accuracy ranged from 82.4 to 128.5% for serum matrix and 90.7 to 127.7% for CSF matrix. All intra- and inter-day coefficients of variation were below 15%. These results demonstrate that the new method is capable of quantifying endogenous serum and CSF levels of a heterogeneous group of compounds spanning a wide range of concentrations. The method was used to determine the physiological levels of target analytes in serum and CSF samples from 18 individuals, demonstrating its reliability and potential usefulness in large-scale epidemiological studies. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Analysis of defense signals in Arabidopsis thaliana leaves by ultra-performance liquid chromatography/tandem mass spectrometry: jasmonates, salicylic acid, abscisic acid.

    PubMed

    Stingl, Nadja; Krischke, Markus; Fekete, Agnes; Mueller, Martin J

    2013-01-01

    Defense signaling compounds and phytohormones play an essential role in the regulation of plant responses to various environmental abiotic and biotic stresses. Among the most severe stresses are herbivory, pathogen infection, and drought stress. The major hormones involved in the regulation of these responses are 12-oxo-phytodienoic acid (OPDA), the pro-hormone jasmonic acid (JA) and its biologically active isoleucine conjugate (JA-Ile), salicylic acid (SA), and abscisic acid (ABA). These signaling compounds are present and biologically active at very low concentrations from ng/g to μg/g dry weight. Accurate and sensitive quantification of these signals has made a significant contribution to the understanding of plant stress responses. Ultra-performance liquid chromatography (UPLC) coupled with a tandem quadrupole mass spectrometer (MS/MS) has become an essential technique for the analysis and quantification of these compounds.

  2. Determination of dasatinib in the tablet dosage form by ultra high performance liquid chromatography, capillary zone electrophoresis, and sequential injection analysis.

    PubMed

    Gonzalez, Aroa Garcia; Taraba, Lukáš; Hraníček, Jakub; Kozlík, Petr; Coufal, Pavel

    2017-01-01

    Dasatinib is a novel oral prescription drug proposed for treating adult patients with chronic myeloid leukemia. Three analytical methods, namely ultra high performance liquid chromatography, capillary zone electrophoresis, and sequential injection analysis, were developed, validated, and compared for determination of the drug in the tablet dosage form. The total analysis time of optimized ultra high performance liquid chromatography and capillary zone electrophoresis methods was 2.0 and 2.2 min, respectively. Direct ultraviolet detection with detection wavelength of 322 nm was employed in both cases. The optimized sequential injection analysis method was based on spectrophotometric detection of dasatinib after a simple colorimetric reaction with folin ciocalteau reagent forming a blue-colored complex with an absorbance maximum at 745 nm. The total analysis time was 2.5 min. The ultra high performance liquid chromatography method provided the lowest detection and quantitation limits and the most precise and accurate results. All three newly developed methods were demonstrated to be specific, linear, sensitive, precise, and accurate, providing results satisfactorily meeting the requirements of the pharmaceutical industry, and can be employed for the routine determination of the active pharmaceutical ingredient in the tablet dosage form. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Advances in ultra-high performance liquid chromatography coupled to tandem mass spectrometry for sensitive detection of several food allergens in complex and processed foodstuffs.

    PubMed

    Planque, M; Arnould, T; Dieu, M; Delahaut, P; Renard, P; Gillard, N

    2016-09-16

    Sensitive detection of food allergens is affected by food processing and foodstuff complexity. It is therefore a challenge to detect cross-contamination in food production that could endanger an allergic customer's life. Here we used ultra-high performance liquid chromatography coupled to tandem mass spectrometry for simultaneous detection of traces of milk (casein, whey protein), egg (yolk, white), soybean, and peanut allergens in different complex and/or heat-processed foodstuffs. The method is based on a single protocol (extraction, trypsin digestion, and purification) applicable to the different tested foodstuffs: chocolate, ice cream, tomato sauce, and processed cookies. The determined limits of quantitation, expressed in total milk, egg, peanut, or soy proteins (and not soluble proteins) per kilogram of food, are: 0.5mg/kg for milk (detection of caseins), 5mg/kg for milk (detection of whey), 2.5mg/kg for peanut, 5mg/kg for soy, 3.4mg/kg for egg (detection of egg white), and 30.8mg/kg for egg (detection of egg yolk). The main advantage is the ability of the method to detect four major food allergens simultaneously in processed and complex matrices with very high sensitivity and specificity. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Determination of pesticide residues in samples of green minor crops by gas chromatography and ultra performance liquid chromatography coupled to tandem quadrupole mass spectrometry.

    PubMed

    Walorczyk, Stanisław; Drożdżyński, Dariusz; Kierzek, Roman

    2015-01-01

    A method was developed for pesticide analysis in samples of high chlorophyll content belonging to the group of minor crops. A new type of sorbent, known as ChloroFiltr, was employed for dispersive-solid phase extraction cleanup (dispersive-SPE) to reduce the unwanted matrix background prior to concurrent analysis by gas chromatography and ultra-performance liquid chromatography coupled to tandem quadrupole mass spectrometry (GC-MS/MS and UPLC-MS/MS). Validation experiments were carried out on green, unripe plants of lupin, white mustard and sorghum. The overall recoveries at the three spiking levels of 0.01, 0.05 and 0.5 mg kg(-1) fell in the range between 68 and 120% (98% on average) and 72-104% (93% on average) with relative standard deviation (RSD) values between 2 and 19% (7% on average) and 3-16% (6% on average) by GC-MS/MS and UPLC-MS/MS technique, respectively. Because of strong enhancement or suppression matrix effects (absolute values >20%) which were exhibited by about 80% of the pesticide and matrix combinations, acceptably accurate quantification was achieved by using matrix-matched standards. Up to now, the proposed method has been successfully used to study the dissipation patterns of pesticides after application on lupin, white mustard, soya bean, sunflower and field bean in experimental plot trials conducted in Poland. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. RECENT ADVANCES IN ULTRA-HIGH PERFORMANCE LIQUID CHROMATOGRAPHY FOR THE ANALYSIS OF TRADITIONAL CHINESE MEDICINE

    PubMed Central

    Huang, Huilian; Liu, Min; Chen, Pei

    2014-01-01

    Traditional Chinese medicine has been widely used for the prevention and treatment of various diseases for thousands of years in China. Ultra-high performance liquid chromatography (UHPLC) is a relatively new technique offering new possibilities. This paper reviews recent developments in UHPLC in the separation and identification, fingerprinting, quantification, and metabolism of traditional Chinese medicine. Recently, the combination of UHPLC with MS has improved the efficiency of the analysis of these materials. PMID:25045170

  6. In vivo study on the neurotransmitters and their metabolites change in depressive disorder rat plasma by ultra high performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Zhao, Longshan; Zheng, Shuning; Su, Guangyue; Lu, Xiumei; Yang, Jingyu; Xiong, Zhili; Wu, Chunfu

    2015-04-15

    A sensitive and versatile, ultra-high performance, liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method coupled to pre-column derivatization for the simultaneous determination of 5-hydroxytryptamine (5-HT), 5-hydroxyindoleacetic acid (5-HIAA), dopamine (DA), norepinephrine (NE), homovanillic acid (HVA), γ-aminobutyric acid (GABA) and glutamic acid (Glu) was developed and validated in rat plasma. The analytes were dansylated under strong alkaline conditions after protein precipitation extraction, which were analyzed on a BEH C18 column using a gradient elution. The lower limit of quantification (LLOQ) values for 5-HT, 5-HIAA, DA, NE, HVA, GABA and Glu were 1.00, 1.00, 0.991, 0.992, 1.02, 1000, and 5030 pmol/mL, respectively. Good linearity was obtained (r > 0.99) and the intra- and inter-day precisions of the method (relative standard deviation, RSD%) were lower than 12%. The method was novel, sensitive and specific which can provide an alternative method for the quantification of neurotransmitters and their metabolites in plasma samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Negative-ion atmospheric pressure ionisation of semi-volatile fluorinated compounds for ultra-high-performance liquid chromatography tandem mass spectrometry analysis.

    PubMed

    Ayala-Cabrera, Juan F; Javier Santos, F; Moyano, Encarnación

    2018-05-24

    In this work, the feasibility of negative-ion atmospheric pressure chemical ionisation (APCI) and atmospheric pressure photoionisation (APPI) for ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) determination of fluorotelomer alcohols (FTOHs), fluorinated octanesulfonamides (FOSAs) and fluorinated octanesulfonamido-ethanols (FOSEs) was evaluated. The study of the effect of mobile phase composition on the atmospheric pressure ionisation of these compounds indicated that methanol/water mixtures provided the best responses in APCI, while acetonitrile/water with a post-column addition of toluene as dopant was the most appropriated mixture in APPI. Under the optimal working conditions, most of the target compounds produced the ion [M-H] - as base peak, although in-source collision-induced dissociation fragment ions in APCI and APPI and superoxide adduct ions [M+O 2 ] -• in APPI were also present. These ions proved to be more useful as precursor ions for MS/MS determination than the adduct ions generated in electrospray. Although the UHPLC-APCI-MS/MS method allowed the determination of these semi-volatile compounds at low concentration levels, the analysis by UHPLC-APPI-MS/MS provided the lowest limits of detection and it was applied to the analysis of water samples in combination with solid-phase extraction. Quality parameters demonstrated the good performance of the proposed method, providing low method limits of detection (0.3-6 ng L -1 ), good precision (RSD % < 5%) and an accurate quantification (relative error % < 14%). Among the river water samples analysed by the developed method, 4:2 FTOH and N-EtFOSA were determined at 30 and 780 ng L -1 , respectively.

  8. [Determination of 49 drugs and 5 metabolites in drinking water samples using ultra-high performance liquid chromatography-electrospray ionization tandem mass spectrometry].

    PubMed

    Wang, Shuo; Zhang, Xiangming; Zhang, Jing; Shao, Bing; Li, Shuming

    2015-07-01

    A method for the determination of 54 drugs in drinking water samples was developed by using ultra-high performance liquid chromatography-electrospray ionization tandem mass spectrometry (UPLC-ESI MS/MS). The target drugs in drinking water samples were enriched and cleaned-up by HLB solid-phase extraction (SPE) cartridges and then eluted with 5 mL methanol. The elute was collected, concentrated under a gentle stream of nitrogen gas, diluted with 0.4 mL 0.1% formic acid solution, and analyzed by UPLC-ESI MS/MS. The separation of the 54 drugs was performed on an ACQUITY UPLC™ BEH C18 column using mobile phases of 0.1% formic acid and methanol by gradient elution. The multiple reaction monitoring (MRM) mode was employed in mass spectrometry acquisition. The matrix-matched external standard calibration was used for quantitation. The results showed that the average recoveries of the drugs in ground water, tap water and surface water were 58.7%-104.4%, 53.1%-109.5%, and 50.7%-118.8%, respectively, and the corresponding relative standard deviations (RSD, n=6) were 0.3%-12.8%, 1.0%-15.5%, and 0.4%-19.3%, respectively. The method quantification limits (MQL) for target compounds were in the range of 0.002-5.000 ng/L. The developed method was applied to analyze the water samples from Beijing. The results showed that 26 drugs were detected in ground water samples.

  9. Ultra-high performance liquid chromatography with tandem mass spectrometry method for the simultaneous quantitation of five phthalides in rat plasma: Application to a comparative pharmacokinetic study of Huo Luo Xiao Ling Dan and herb-pair extract.

    PubMed

    Ma, Wen; Wang, Weihui; Peng, Yan; Bian, Qiaoxia; Wang, Nannan; Lee, David Y-W; Dai, Ronghua

    2016-06-01

    A fast, sensitive, and reliable ultra-high performance liquid chromatography with tandem mass spectrometry method has been developed and validated for the simultaneous quantitation and pharmacokinetic study of five phthalides (senkyunolide A, ligustilide, butylidenephthalide, 3-butylphthalide, and levistilide A) in rat plasma after oral administration of Huo Luo Xiao Ling Dan (HLXLD) or Angelica sinensis--Ligusticum chuanxiong herb pair (DG-CX) between normal and arthritis rats. After extraction from blood, the analytes and internal standard were subjected to ultra-high performance liquid chromatography with a Shim-pack XR-ODS column (75 × 3.0 mm(2) , 2.2 μm particles) and mobile phase was composed of methanol and water (containing 0.05% formic acid) under gradient elution conditions, with an electrospray ionization source in the positive ionization and multiple reaction monitoring mode. The lower limits of quantification were 0.192-0.800 ng/mL for all the analytes. Satisfactory linearity, precision, accuracy, mean extraction recovery, and acceptable matrix effect have been achieved. The validated method was successfully applied to a comparative pharmacokinetic study of five bioactive components in rat plasma after oral administration of HLXLD or DG-CX alone, respectively, between normal and arthritic rats. The results showed that there were unlike characters of pharmacokinetics among different groups. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. High-performance liquid chromatography coupled with tandem mass spectrometry technology in the analysis of Chinese Medicine Formulas: A bibliometric analysis (1997-2015).

    PubMed

    He, Xi-Ran; Li, Chun-Guang; Zhu, Xiao-Shu; Li, Yuan-Qing; Jarouche, Mariam; Bensoussan, Alan; Li, Ping-Ping

    2017-01-01

    There is a recognized challenge in analyzing traditional Chinese medicine formulas because of their complex chemical compositions. The application of modern analytical techniques such as high-performance liquid chromatography coupled with a tandem mass spectrometry has improved the characterization of various compounds from traditional Chinese medicine formulas significantly. This study aims to conduct a bibliometric analysis to recognize the overall trend of high-performance liquid chromatography coupled with tandem mass spectrometry approaches in the analysis of traditional Chinese medicine formulas, its significance and possible underlying interactions between individual herbs in these formulas. Electronic databases were searched systematically, and the identified studies were collected and analyzed using Microsoft Access 2010, Graph Pad 5.0 software and Ucinet software package. 338 publications between 1997 and 2015 were identified, and analyzed in terms of annual growth and accumulated publications, top journals, forms of traditional Chinese medicine preparations and highly studied formulas and single herbs, as well as social network analysis of single herbs. There is a significant increase trend in using high-performance liquid chromatography coupled with tandem mass spectrometry related techniques in analysis of commonly used forms of traditional Chinese medicine formulas in the last 3 years. Stringent quality control is of great significance for the modernization and globalization of traditional Chinese medicine, and this bibliometric analysis provided the first and comprehensive summary within this field. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Determination of 15 N-nitrosodimethylamine precursors in different water matrices by automated on-line solid-phase extraction ultra-high-performance-liquid chromatography tandem mass spectrometry.

    PubMed

    Farré, Maria José; Insa, Sara; Mamo, Julian; Barceló, Damià

    2016-08-05

    A new methodology based on on-line solid-phase extraction (SPE) ultra-high-performance-liquid chromatography coupled to a triple quadrupole mass spectrometer (UHPLC-MS-MS) for the determination of 15 individual anthropogenic N-nitrosodimethylamine (NDMA) precursors was developed. On-line SPE was performed by passing 2mL of the water sample through a Hypersil GOLD aQ column and chromatographic separation was done using a Kinetex Biphenyl column using methanol and 0.1% formic acid aqueous solution as a mobile phase. For unequivocal identification and confirmation, two selected reaction monitoring (SRM) transitions were monitored per compound. Quantification was performed by internal standard approach and matrix match calibration. The main advantages of the developed method are high sensitivity (limits of detection in the sub ng/L range), selectivity due to the use of tandem mass spectrometry, precision and minimum sample manipulation as well as fast analytical response. Process efficiency and recovery were also evaluated for all the target compounds. As part of the validation procedure, the method was applied in a sampling campaign for the analysis of influent and secondary effluent of a wastewater treatment plant (WWTP) in Girona, Spain. Additionally, the effluent from a nanofiltration (NF) membrane system used for water recycling was monitored. The percentage of NDMA formation explained by the measured precursors was also quantified. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. [Analysis of picric acid and picramic acid in water samples by ultra performance hydrophilic interaction chromatography-tandem mass spectrometry].

    PubMed

    Qian, Feizhong; Zhu, Libo; Xu, Nengbin; Feng, Jiayong; Hong, Zhengfang; Xu, Lihong; Chen, Zhongquan; Wang, Shengle

    2014-05-01

    An ultra performance liquid chromatography/tandem mass spectrometry (UPLC-MS/ MS) method was developed for the determination of picric acid and its reductive transformation product picramic acid in aqueous samples. A hydrophilic interaction liquid chromatography (HILIC) column (Acquity UPLC BEH HILIC; 100 mm x 2.1 mm, 1.7 microm) was used for the separation. Surface water samples could be injected into the UPLC system just after being filtered through a 0.2 microm membrane. The satisfactory recoveries of picric acid and picramic acid were in the range of 89% - 107%. Waste water samples were purified by solid phase extraction (SPE), and then were analyzed. The recoveries of picric acid and picramic acid in waste water were 72%-101%. The reproducibility of the method was good with the RSDs of 4.9% - 14.7%. The limits of detection (LODs) of picric acid and picramic acid were 0.1 microg/L and 0.3 microg/L, respectively. This proposed method is rapid, highly specific and suitable for the confirmation and quantitative determination of picric acid and picramic acid in surface water and waste water.

  13. [Simultaneous determination of delta-9-tetrahydrocannabinol cannabidiol and cannabinol in edible oil using ultra performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Zhang, Aizhi; Wang, Quanlin; Mo, Shijie

    2010-11-01

    A method for the simultaneous determination of delta-9-tetrahydrocannabinol (THC), cannabidiol (CBD) and cannabinol (CBN) in edible oil was developed using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The target compounds were extracted with methanol, purified by an LC-Alumina-N solid phase extraction cartridge, separated and detected by the UPLC-MS/MS. Quantitative analysis was corrected by an isotope internal standard method using delta-9-THC-D3 as internal standard. Average recoveries for the target compounds varied from 68.0% to 101.6% with the relative standard deviations ranging from 7.0% to 20.1% at three spiked levels. The limits of detection (LOD) of the method were from 0.06-0.17 microg/kg and the limits of quantification (LOQ) were in the range of 0.20-0.52 microg/kg. The results showed that the method is able to meet the requirements for the simultaneous determination of THC, CBD and CBN in edible oil.

  14. Simultaneous detection and quantitation of organic impurities in methamphetamine by ultra-high-performance liquid chromatography-tandem mass spectrometry, a complementary technique for methamphetamine profiling.

    PubMed

    Li, Li; Brown, Jaclyn L; Toske, Steven G

    2018-04-06

    The analysis of organic impurities plays an important role in the impurity profiling of methamphetamine, which in turn provides valuable information about methamphetamine manufacturing, in particular its synthetic route, chemicals, and precursors used. Ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) is ideally suited for this purpose due to its excellent sensitivity, selectivity, and wide linear range in multiple reaction monitoring (MRM) mode. In this study, a dilute-and-shoot UHPLC-MS/MS method was developed for the simultaneous identification and quantitation of 23 organic manufacturing impurities in illicit methamphetamine. The developed method was validated in terms of stability, limit of detection (LOD), lower limit of quantification (LLOQ), accuracy, and precision. More than 100 illicitly prepared methamphetamine samples were analyzed. Due to its ability to detect ephedrine/pseudoephedrine and its high sensitivity for critical target markers (eg, chloro-pseudoephedrine, N-cyclohexylamphetamine, and compounds B and P), more impurities and precursor/pre-precursors were identified and quantified versus the current procedure by gas chromatography-mass spectrometry (GC-MS). Consequently, more samples could be classified by their synthetic routes. However, the UHPLC-MS/MS method has difficulty in detecting neutral and untargeted emerging manufacturing impurities and can therefore only serve as a complement to the current method. Despite this deficiency, the quantitative information acquired by the presented UHPLC-MS/MS methodology increased the sample discrimination power, thereby enhancing the capacity of methamphetamine profiling program (MPP) to conduct sample-sample comparisons. Published 2018. This article is a U.S. Government work and is in the public domain in the USA.

  15. Development and validation of amitriptyline and its metabolite in human plasma by ultra performance liquid chromatography-tandem mass spectrometry and its application to a bioequivalence study.

    PubMed

    Bhatt, Mitesh; Shah, Sanjay

    2010-11-01

    A method based on ultra performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) in combination with solid-phase extraction for sample pretreatment has been developed for the simultaneous analysis of amitriptyline and its main metabolite in human plasma. The extraction of the analytes from plasma samples was carried out by means of a selective SPE procedure using hydrophilic-lipophilic balance cartridges. The assay involves a simple solid-phase extraction (SPE) procedure of 0.2 mL of human plasma and analysis was performed on a triple-quadrupole tandem mass spectrometer by multiple reactions monitoring (MRM) mode via electrospray ionization (ESI). The standard calibration curve was linear over the ranges 0.370-95.539 ng/mL for amitriptyline and 0.365-94.374 ng/mL for nortriptyline, expressed by the linear correlation coefficient r², which was better than 0.995 for both. The intra- and inter-day precision and accuracy of the quality control samples were within 10.0%. The recovery was 85.3, 88.4 and 80.7% for amitriptyline, nortriptyline and doxepin respectively. Total run time was 1.2 min only for each sample, which makes it possible to analyze more than 400 samples per day. The method was highly reproducible and gave peaks with excellent chromatography properties. Copyright © 2010 John Wiley & Sons, Ltd.

  16. Simultaneous determination of bisphenols and alkylphenols in water by solid phase extraction and ultra performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Shan, Xiao Mei; Shen, Deng Hui; Wang, Bing Shuang; Lu, Bei Bei; Huang, Fa Yuan

    2014-06-01

    To establish an analytical method for determination of four bisphenols (BPA, BPB, BPF, and BPS) and two alkylphenols (4-n-OP, 4-n-NP) in water by ultra performance liquid chromatography- tandem mass spectrometry (UPLC/MS/MS). The water samples were extracted and condensed with solid-phase extraction (SPE) using C18 cartridges and eluted by acetonitrile. Separation was carried out with Acquity BEH C8 column and detection were performed by UPLC/MS/MS. Quantification was calculated by using the internal standard BPA-d16 and 4-n-NP-d8. The linear correlation coefficients of these compounds in the range of 1.0-100.0 μg/L were all over 0.999. The minimum detectable concentrations were 0.75-1.0 ng/L, and the recoveries ranged from 87.0% to 106.9%. Relative standard deviations (RSDs) were between 1.26% and 3.67%. Applying this method to detect the source water of Chaohu Lake and drinking water of Hefei, six target compounds were detected in different levels. This method is simple with high sensitivity and selectivity, could be suitable for the determination of these compounds in source and drinking water. Copyright © 2014 The Editorial Board of Biomedical and Environmental Sciences. Published by China CDC. All rights reserved.

  17. Ultra-sensitive high performance liquid chromatography-laser-induced fluorescence based proteomics for clinical applications.

    PubMed

    Patil, Ajeetkumar; Bhat, Sujatha; Pai, Keerthilatha M; Rai, Lavanya; Kartha, V B; Chidangil, Santhosh

    2015-09-08

    An ultra-sensitive high performance liquid chromatography-laser induced fluorescence (HPLC-LIF) based technique has been developed by our group at Manipal, for screening, early detection, and staging for various cancers, using protein profiling of clinical samples like, body fluids, cellular specimens, and biopsy-tissue. More than 300 protein profiles of different clinical samples (serum, saliva, cellular samples and tissue homogenates) from volunteers (normal, and different pre-malignant/malignant conditions) were recorded using this set-up. The protein profiles were analyzed using principal component analysis (PCA) to achieve objective detection and classification of malignant, premalignant and healthy conditions with high sensitivity and specificity. The HPLC-LIF protein profiling combined with PCA, as a routine method for screening, diagnosis, and staging of cervical cancer and oral cancer, is discussed in this paper. In recent years, proteomics techniques have advanced tremendously in life sciences and medical sciences for the detection and identification of proteins in body fluids, tissue homogenates and cellular samples to understand biochemical mechanisms leading to different diseases. Some of the methods include techniques like high performance liquid chromatography, 2D-gel electrophoresis, MALDI-TOF-MS, SELDI-TOF-MS, CE-MS and LC-MS techniques. We have developed an ultra-sensitive high performance liquid chromatography-laser induced fluorescence (HPLC-LIF) based technique, for screening, early detection, and staging for various cancers, using protein profiling of clinical samples like, body fluids, cellular specimens, and biopsy-tissue. More than 300 protein profiles of different clinical samples (serum, saliva, cellular samples and tissue homogenates) from healthy and volunteers with different malignant conditions were recorded by using this set-up. The protein profile data were analyzed using principal component analysis (PCA) for objective

  18. Fast quantification of ten psychotropic drugs and metabolites in human plasma by ultra-high performance liquid chromatography tandem mass spectrometry for therapeutic drug monitoring.

    PubMed

    Ansermot, Nicolas; Brawand-Amey, Marlyse; Kottelat, Astrid; Eap, Chin B

    2013-05-31

    A sensitive and selective ultra-high performance liquid chromatography (UHPLC) tandem mass spectrometry (MS/MS) method was developed for the fast quantification of ten psychotropic drugs and metabolites in human plasma for the needs of our laboratory (amisulpride, asenapine, desmethyl-mirtazapine, iloperidone, mirtazapine, norquetiapine, olanzapine, paliperidone, quetiapine and risperidone). Stable isotope-labeled internal standards were used for all analytes, to compensate for the global method variability, including extraction and ionization variations. Sample preparation was performed by generic protein precipitation with acetonitrile. Chromatographic separation was achieved in less than 3.0min on an Acquity UPLC BEH Shield RP18 column (2.1mm×50mm; 1.7μm), using a gradient elution of 10mM ammonium formate buffer pH 3.0 and acetonitrile at a flow rate of 0.4ml/min. The compounds were quantified on a tandem quadrupole mass spectrometer operating in positive electrospray ionization mode, using multiple reaction monitoring. The method was fully validated according to the latest recommendations of international guidelines. Eight point calibration curves were used to cover a large concentration range 0.5-200ng/ml for asenapine, desmethyl-mirtazapine, iloperidone, mirtazapine, olanzapine, paliperidone and risperidone, and 1-1500ng/ml for amisulpride, norquetiapine and quetiapine. Good quantitative performances were achieved in terms of trueness (93.1-111.2%), repeatability (1.3-8.6%) and intermediate precision (1.8-11.5%). Internal standard-normalized matrix effects ranged between 95 and 105%, with a variability never exceeding 6%. The accuracy profiles (total error) were included in the acceptance limits of ±30% for biological samples. This method is therefore suitable for both therapeutic drug monitoring and pharmacokinetic studies. Copyright © 2013 Elsevier B.V. All rights reserved.

  19. Simultaneous determination of nine neonicotinoids in human urine using isotope-dilution ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhang, Quan; Wang, Ximing; Li, Zhe; Jin, Hangbiao; Lu, Zhengbiao; Yu, Chang; Huang, Yu-Fang; Zhao, Meirong

    2018-05-14

    Neonicotinoids (neonics), a class of systemic insecticides, have been frequently detected in pollen, vegetables, and fruits. Recently, an increasing concern has been aroused for human exposure to neonics. However, biological monitoring for quantifying body burden of neonics has rarely been reported. In this study, we developed an isotope-dilution ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) method to simultaneously quantify nine neonics, including acetamiprid (ACE), thiamethoxam (THIAM), imidacloprid (IMIP), clothianidin (CLO), flonicamid (FLO), thiacloprid (THIAC), dinotefuran (DIN), nitenpyram (NIT), and imidaclothiz (IMIT) in urine. The limits of quantification were 0.1 μg/L for ACE, FLO, DIN, NIT and IMIT, and 0.2 μg/L for THIAM, IMIP, CLO, and THIAC. The overall recoveries were 80.8-103%, 81.5-91.7% and 83.0-92.3% for QA/QC samples fortifying at 1, 25, and 100 μg/L levels, respectively. UPLC/MS/MS method was used to analyze urine samples obtained from 10 children in Hangzhou, China. The detection frequencies were 80% for ACE and IMIP, 70% for THIAM and CLO, 20% for DIN and IMIT and 10% for THIAC. FLO and NIT were not detected in those urine samples. The data provided here will be helpful for conducting biological monitoring of neonics exposure in the future. Copyright © 2018 Elsevier Ltd. All rights reserved.

  20. Development and validation of rapid multiresidue and multi-class analysis for antibiotics and anthelmintics in feed by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Robert, Christelle; Brasseur, Pierre-Yves; Dubois, Michel; Delahaut, Philippe; Gillard, Nathalie

    2016-08-01

    A new multi-residue method for the analysis of veterinary drugs, namely amoxicillin, chlortetracycline, colistins A and B, doxycycline, fenbendazole, flubendazole, ivermectin, lincomycin, oxytetracycline, sulfadiazine, tiamulin, tilmicosin and trimethoprim, was developed and validated for feed. After acidic extraction, the samples were centrifuged, purified by SPE and analysed by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry. Quantitative validation was done in accordance with the guidelines laid down in European Commission Decision 2002/657/CE. Matrix-matched calibration with internal standards was used to reduce matrix effects. The target level was set at the authorised carryover level (1%) and validation levels were set at 0.5%, 1% and 1.5%. Method performances were evaluated by the following parameters: linearity (0.986 < R(2) < 0.999), precision (repeatability < 12.4% and reproducibility < 14.0%), accuracy (89% < recovery < 107%), sensitivity, decision limit (CCα), detection capability (CCβ), selectivity and expanded measurement uncertainty (k = 2).This method has been used successfully for three years for routine monitoring of antibiotic residues in feeds during which period 20% of samples were found to exceed the 1% authorised carryover limit and were deemed non-compliant.

  1. Integration of Electrochemistry with Ultra Performance Liquid Chromatography/Mass Spectrometry (UPLC/MS)

    PubMed Central

    Cai, Yi; Zheng, Qiuling; Liu, Yong; Helmy, Roy; Loo, Joseph A.; Chen, Hao

    2015-01-01

    This study presents the development of ultra-performance liquid chromatography/mass spectrometry (UPLC/MS) combined with electrochemistry (EC) for the first time and its application for the structural analysis of disulfide bond-containing proteins/peptides. In our approach, a protein/peptide mixture sample undergoes fast UPLC separation and subsequent electrochemical reduction in an electrochemical flow cell followed by online MS and MS/MS analyses. The electrochemical cell is coupled to MS using our recently developed desorption electrospray ionization (DESI) interface. Using this UPLC/EC/DESI-MS method, disulfide bond-containing peptides can be differentiated from those without disulfide bonds as the former are electroactive and reducible. Tandem MS analysis of the disulfide-reduced peptide ions provides increased sequence and disulfide linkage pattern information. In a reactive DESI-MS detection experiment in which a supercharging reagent was used to dope the DESI spray solvent, increased charging was obtained for the UPLC-separated proteins. Strikingly, upon online electrolytic reduction, supercharged proteins (e.g., α-lactalbumin) showed even higher charging, which would be useful in top-down protein structure analysis as increased charges are known to promote protein ion dissociation. Also, the separation speed and sensitivity are enhanced by approximately 1~2 orders of magnitude by using UPLC for the LC/EC/MS platform, in comparison to the previously used high performance liquid chromatography (HPLC). This UPLC/EC/DESI-MS method combines the power of fast UPLC separation, fast electrochemical conversion and online MS structural analysis for a potentially valuable tool for proteomics research and bioanalysis. PMID:26307715

  2. Simultaneous determination of 12 pharmaceuticals in water samples by ultrasound-assisted dispersive liquid-liquid microextraction coupled with ultra-high performance liquid chromatography with tandem mass spectrometry.

    PubMed

    Guan, Jin; Zhang, Chi; Wang, Yang; Guo, Yiguang; Huang, Peiting; Zhao, Longshan

    2016-11-01

    A new analytical method was developed for simultaneous determination of 12 pharmaceuticals using ultrasound-assisted dispersive liquid-liquid microextraction (DLLME) followed by ultra-high performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS). Six nonsteroidal anti-inflammatory drugs (NSAIDs, ketoprofen, mefenamic acid, tolfenamic acid, naproxen, sulindac, and piroxicam) and six antibiotics (tinidazole, cefuroxime axetil, ciprofloxacin, sulfamethoxazole, sulfadiazine, and chloramphenicol) were extracted by ultrasound-assisted DLLME using dichloromethane (800 μL) and methanol/acetonitrile (1:1, v/v, 1200 μL) as the extraction and dispersive solvents, respectively. The factors affecting the extraction efficiency, such as the type and volume of extraction and dispersive solvent, vortex and ultrasonic time, sample pH, and ionic strength, were optimized. The ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution by using a small volume of dispersive solvent, which increased the extraction efficiency and reduced the equilibrium time. Under the optimal conditions, the calibration curves showed good linearity in the range of 0.04-20 ng mL -1 (ciprofloxacin and sulfadiazine), 0.2-100 ng mL -1 (ketoprofen, tinidazole, cefuroxime axetil, naproxen, sulfamethoxazole, and sulindac), and 1-200 ng mL -1 (mefenamic acid, tolfenamic acid, piroxicam, and chloramphenicol). The LODs and LOQs of the method were in the range of 0.006-0.091 and 0.018-0.281 ng mL -1 , respectively. The relative recoveries of the target analytes were in the range from 76.77 to 99.97 % with RSDs between 1.6 and 8.8 %. The developed method was successfully applied to the extraction and analysis of 12 pharmaceuticals in five kinds of water samples (drinking water, running water, river water, influent and effluent wastewater) with satisfactory results. Graphical Abstract Twelve pharmaceuticals in water samples analyted by UHPLC

  3. Fast analysis of 29 polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs with ultra-high performance liquid chromatography-atmospheric pressure photoionization-tandem mass spectrometry

    PubMed Central

    Lung, Shih-Chun Candice; Liu, Chun-Hu

    2015-01-01

    Polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs are ubiquitous in the environment. Some of them are probable carcinogens and some are source markers. This work presents an ultra-high performance liquid chromatography-atmospheric pressure photoionization-tandem mass spectrometry (UHPLC-APPI-MS/MS) method for simultaneous analysis of 20 PAHs and nine nitro-PAHs. These compounds are separated in 15 minutes in the positive mode and 11 minutes in the negative mode, one half of GC/MS analysis time. Two pairs of precursor/product ions are offered, which is essential for confirmation. This method separates and quantifies benzo[a]pyrene (the most toxic PAHs) and non-priority benzo[e]pyrene (isomers, little toxicity) to avoid overestimation of toxin levels, demonstrating its importance for health-related researches. With 0.5% 2,4-difluoroanisole in chlorobenzene as the dopant, limits of detection of PAHs except acenaphthylene and those of nitro-PAHs except 2-nitrofluoranthene are below 10 pg and 3 pg, respectively, mostly lower than or comparable to those reported using LC-related systems. The responses were linear over two orders of magnitude with fairly good accuracy and precision. Certified reference materials and real aerosol samples were analyzed to demonstrate its applicability. This fast, sensitive, and reliable method is the first UHPLC-APPI-MS/MS method capable of simultaneously analyzing 29 environmentally and toxicologically important PAHs and nitro-PAHs. PMID:26265155

  4. Quantification of sulphur amino acids by ultra-high performance liquid chromatography in aquatic invertebrates.

    PubMed

    Thera, Jennifer C; Kidd, Karen A; Dodge-Lynch, M Elaine; Bertolo, Robert F

    2017-12-15

    We examined the performance of an ultra-high performance liquid chromatography method to quantify protein-bound sulphur amino acids in zooplankton. Both cysteic acid and methionine sulfone were linear from 5 to 250 pmol (r 2  = 0.99), with a method detection limit of 13 pmol and 9 pmol, respectively. Although there was no matrix effect on linearity, adjacent peaks and co-eluting noise from the invertebrate proteins increased the detection limits when compared to common standards. Overall, performance characteristics were reproducible and accurate, and provide a means for quantifying sulphur amino acids in aquatic invertebrates, an understudied group. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. Peptide profiling of Internet-obtained Cerebrolysin using high performance liquid chromatography - electrospray ionization ion trap and ultra high performance liquid chromatography - ion mobility - quadrupole time of flight mass spectrometry.

    PubMed

    Gevaert, Bert; D'Hondt, Matthias; Bracke, Nathalie; Yao, Han; Wynendaele, Evelien; Vissers, Johannes Petrus Cornelis; De Cecco, Martin; Claereboudt, Jan; De Spiegeleer, Bart

    2015-09-01

    Cerebrolysin, a parenteral peptide preparation produced by controlled digestion of porcine brain proteins, is an approved nootropic medicine in some countries. However, it is also easily and globally available on the Internet. Nevertheless, until now, its exact chemical composition was unknown. Using high performance liquid chromatography (HPLC) coupled to ion trap and ultra high performance liquid chromatography (UHPLC) coupled to quadrupole-ion mobility-time-of-flight mass spectrometry (Q-IM-TOF MS), combined with UniProt pig protein database search and PEAKS de novo sequencing, we identified 638 unique peptides in an Internet-obtained Cerebrolysin sample. The main components in this sample originate from tubulin alpha- and beta-chain, actin, and myelin basic protein. No fragments of known neurotrophic factors like glial cell-derived neurotrophic factor (GDNF), neurotrophin nerve growth factor (NGF), brain-derived neurotrophic factor (BDNF), and ciliary neurotrophic factor (CNTF) were found, suggesting that the activities reported in the literature are likely the result of new, hitherto unknown cryptic peptides with nootropic properties. Copyright © 2015 John Wiley & Sons, Ltd.

  6. Development and validation of an ultra high performance liquid chromatography electrospray ionization tandem mass spectrometry method for the simultaneous determination of selected flavonoids in Ginkgo biloba.

    PubMed

    Pandey, Renu; Chandra, Preeti; Arya, Kamal Ram; Kumar, Brijesh

    2014-12-01

    A rapid and sensitive ultra high performance liquid chromatography electrospray ionization tandem mass spectrometry method was developed and validated for the simultaneous determination of 13 flavonoids in leaf, stem, and fruit extracts of male and female trees of Ginkgo biloba to investigate gender- and age-related variations of flavonoids content. Chromatographic separation was accomplished on an Acquity UPLC BEH C18 column (50 mm × 2.1 mm id, 1.7 μm) in 5 min. Quantitation was performed using negative electrospray ionization mass spectrometry in multiple reaction monitoring mode. The calibration curves of all analytes showed a good linear relationship (r(2) ≥ 0.9977) over the concentration range of 1-1000 ng/mL. The precision evaluated by an intra- and interday study showed RSD ≤ 1.98% and good accuracy with overall recovery in the range from 97.90 to 101.09% (RSD ≤ 1.67%) for all analytes. The method sensitivity expressed as the limit of quantitation was typically 0.25-3.57 ng/mL. The results showed that the total content of 13 flavonoids was higher in the leaf extract of an old male Ginkgo tree compared to young female Ginkgo trees. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Rapid residue analysis of four triazolopyrimidine herbicides in soil, water, and wheat by ultra-performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Liu, Xingang; Xu, Jun; Li, Yuanbo; Dong, Fengshou; Li, Jing; Song, Wenchen; Zheng, Yongquan

    2011-03-01

    A sensitive and effective method for simultaneous determination of triazolopyrimidine sulfonamide herbicide residues in soil, water, and wheat was developed using ultra-performance liquid chromatography coupled with tandem mass spectrometry. The four herbicides (pyroxsulam, flumetsulam, metosulam, and diclosulam) were cleaned up with an off-line C18 SPE cartridge and detected by tandem mass spectrometry using an electrospray ionization source in positive mode (ESI+). The determination of the target compounds was achieved in <2.0 min. The limits of detection were below 1 μg kg(-1), while the limits of quantification did not exceed 3 μg kg(-1) in different matrices. Quantitation was determined from calibration curves of standards containing 0.05-100 μg L(-1) with r(2) > 0.997. Recovery studies were conducted at three spiked levels (0.2, 1, and 5 μg kg(-1) for water; 5, 10, and 100 μg kg(-1) for soil and wheat). The overall average recoveries for this method in water, soil, wheat plants, and seeds at three levels ranged from 75.4% to 106.0%, with relative standard deviations in the range of 2.1-12.5% (n = 5) for all analytes.

  8. Urinary metabolomic profiling in rats exposed to dietary di(2-ethylhexyl) phthalate (DEHP) using ultra-performance liquid chromatography quadrupole time-of-flight tandem mass spectrometry (UPLC/Q-TOF-MS).

    PubMed

    Dong, Xinwen; Zhang, Yunbo; Dong, Jin; Zhao, Yue; Guo, Jipeng; Wang, Zhanju; Liu, Mingqi; Na, Xiaolin; Wang, Cheng

    2017-07-01

    Di(2-ethylhexyl) phthalate (DEHP) is an omnipresent environmental chemical with widespread nonoccupational human exposure through multiple ways. Although considerable efforts have been invested to investigate mechanisms of DEHP toxicity, the key metabolic biomarkers of DEHP toxicity remain to be identified. The aim of this study was to assess the urinary metabonomics of dietary DEHP in rats using the technique of ultra-performance liquid chromatography quadrupole time-of-flight tandem mass spectrometry (UPLC/Q-TOF-MS). Fourteen female Wistar rats were divided into two groups and given increasing dietary doses of DEHP for 30 consecutive days. The urinary metabolite profile was studied using ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry. Principal component analysis (PCA) and partial least squares-discriminant analysis (PLS-DA) enabled clusters to be clearly separated. Eleven principal urinary metabolites were identified as contributing to the clusters. The clusters in the positive electrospray ionization (ESI) mode were xanthurenic acid, kynurenic acid, nonate, N6-methyladenosine, and L-isoleucyl-L-proline. The clusters in the negative ESI mode were hippuric acid, tetrahydrocortisol, citric acid, phenylpropionylglycine, cPA(18:2(9Z, 12Z)/0:0), and LysoPC(14:1(9Z)). The urinary metabonomic changes indicated that exposure to dietary DEHP can affect energy-related metabolism, liver and renal function, fatty acid metabolism, and cause DNA damage in rats. The findings of this study on the urinary metabolites and metabolic pathways of DEHP may form the basis for future studies on the mechanisms of toxicity of this commonly found environmental chemical.

  9. A new combined method of stable isotope-labeling derivatization-ultrasound-assisted dispersive liquid-liquid microextraction for the determination of neurotransmitters in rat brain microdialysates by ultra high performance liquid chromatography tandem mass spectrometry.

    PubMed

    Zheng, Longfang; Zhao, Xian-En; Zhu, Shuyun; Tao, Yanduo; Ji, Wenhua; Geng, Yanling; Wang, Xiao; Chen, Guang; You, Jinmao

    2017-06-01

    In this work, for the first time, a new hyphenated technique of stable isotope-labeling derivatization-ultrasound-assisted dispersive liquid-liquid microextraction has been developed for the simultaneous determination of monoamine neurotransmitters (MANTs) and their biosynthesis precursors and metabolites. The developed method was based on ultra high performance liquid chromatography tandem mass spectrometry detection using multiple-reaction monitoring mode. A pair of mass spectrometry sensitizing reagents, d 0 -10-methyl-acridone-2-sulfonyl chloride and d 3 -10-methyl-acridone-2-sulfonyl chloride, as stable isotope probes was utilized to facilely label neurotransmitters, respectively. The heavy labeled MANTs standards were prepared and used as internal standards for quantification to minimize the matrix effects in mass spectrometry analysis. Low toxic bromobenzene (extractant) and acetonitrile (dispersant) were utilized in microextraction procedure. Under the optimized conditions, good linearity was observed with the limits of detection (S/N>3) and limits of quantification (S/N>10) in the range of 0.002-0.010 and 0.015-0.040nmol/L, respectively. Meanwhile, it also brought acceptable precision (4.2-8.8%, peak area RSDs %) and accuracy (recovery, 96.9-104.1%) results. This method was successfully applied to the simultaneous determination of monoamine neurotransmitters and their biosynthesis precursors and metabolites in rat brain microdialysates of Parkinson's disease and normal rats. This provided a new method for the neurotransmitters related studies in the future. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Determination of artemisitene in rat plasma by ultra-performance liquid chromatography/tandem mass spectrometry and its application in pharmacokinetics.

    PubMed

    Wu, Li-Lan; Wu, Yun-Shan; Chen, Wei-Ying; Zhou, Wen; Tang, Lipeng; Li, Ben; Liu, Bo

    2017-07-15

    Artemisitene shows a wide variety of pharmacological activities, such as antioxidant protection in vitro and in vivo. It has been identified as a novel Nrf2 inducer. However, there is no report on an ultra-performance liquid chromatography/tandem mass spectrometry (UPLC/MS/MS) method to quantitate artemisitene in rat plasma and its application to a pharmacokinetic profile study. An ACQUITY UPLC™ BEH Symmetry Shield RP18 column (1.7 μm, 2.1 mm × 100 mm) was used at a flow rate of 0.3 mL·min -1 . Mass detection was performed by electrospray ionization tandem mass spectrometry via multiple reaction monitoring (MRM) in positive mode. Plasma samples were pre-treated by a single-step extraction with 0.1% formic acid aqueous solutions-acetonitrile, and tolbutamide was used as internal standard. The calibration curve was from 0.98 to 1000 ng∙mL -1 (r 2  = 0.995). The extraction recoveries were 61.5-79.4% and 81.7-94.6% for artemisitene and tolbutamide, respectively. The lower limit of quantification (LLOQ) was 0.98 ng∙mL -1 . The absolute bioavailability of artemisitene was 3.7% after intravenous and oral administration in rats. The UPLC/MS/MS assay was validated for linearity, accuracy, stability, extraction recovery, matrix effects, and intra-day and inter-day precision. The method, for the first time, achieved some pharmacokinetic parameters and was successfully applied to a pharmacokinetic study Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  11. A Method for Multiple Mycotoxin Analysis in Wines by Solid Phase Extraction and Multifunctional Cartridge Purification, and Ultra-High-Performance Liquid Chromatography Coupled to Tandem Mass Spectrometry

    PubMed Central

    Tamura, Masayoshi; Takahashi, Ayumi; Uyama, Atsuo; Mochizuki, Naoki

    2012-01-01

    An analytical method using two solid phase extractions and ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) was developed for the identification and quantification of 14 mycotoxins (patulin, deoxynivalenol, aflatoxins B1, B2, G1, G2, M1, T-2 toxin, HT-2 toxin, zearalenone, fumonisins B1, B2, B3, and ochratoxin A) in domestic and imported wines. Mycotoxins were purified with an Oasis HLB cartridge, followed by a MultiSepTM #229 Ochra. As a result, sufficient removal of the pigments and highly polar matrices from the red wines was achieved. UHPLC conditions were optimized, and 14 mycotoxins were separated in a total of 13 min. Determinations performed using this method produced high correlation coefficients for the 14 mycotoxins (R > 0.990) and recovery rates ranging from 76 to 105% with good repeatability (relative standard deviation RSD < 12%). Twenty-seven samples of domestic and imported wines were analyzed using this method. Although ochratoxin A (OTA) and fumonisins (FMs) were detected in several samples, the FM levels were less than limits of quantification (LOQs) (1 μg/L), and even the largest of the OTA levels was below the EU regulatory level (2 μg/L). These results suggest that the health risk posed to consumers from the wines available in Japan is relatively low. PMID:22822458

  12. Two-way and three-way approaches to ultra high performance liquid chromatography-photodiode array dataset for the quantitative resolution of a two-component mixture containing ciprofloxacin and ornidazole.

    PubMed

    Dinç, Erdal; Ertekin, Zehra Ceren; Büker, Eda

    2016-09-01

    Two-way and three-way calibration models were applied to ultra high performance liquid chromatography with photodiode array data with coeluted peaks in the same wavelength and time regions for the simultaneous quantitation of ciprofloxacin and ornidazole in tablets. The chromatographic data cube (tensor) was obtained by recording chromatographic spectra of the standard and sample solutions containing ciprofloxacin and ornidazole with sulfadiazine as an internal standard as a function of time and wavelength. Parallel factor analysis and trilinear partial least squares were used as three-way calibrations for the decomposition of the tensor, whereas three-way unfolded partial least squares was applied as a two-way calibration to the unfolded dataset obtained from the data array of ultra high performance liquid chromatography with photodiode array detection. The validity and ability of two-way and three-way analysis methods were tested by analyzing validation samples: synthetic mixture, interday and intraday samples, and standard addition samples. Results obtained from two-way and three-way calibrations were compared to those provided by traditional ultra high performance liquid chromatography. The proposed methods, parallel factor analysis, trilinear partial least squares, unfolded partial least squares, and traditional ultra high performance liquid chromatography were successfully applied to the quantitative estimation of the solid dosage form containing ciprofloxacin and ornidazole. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Integrating qualitative and quantitative characterization of traditional Chinese medicine injection by high-performance liquid chromatography with diode array detection and tandem mass spectrometry.

    PubMed

    Xie, Yuan-yuan; Xiao, Xue; Luo, Juan-min; Fu, Chan; Wang, Qiao-wei; Wang, Yi-ming; Liang, Qiong-lin; Luo, Guo-an

    2014-06-01

    The present study aims to describe and exemplify an integrated strategy of the combination of qualitative and quantitative characterization of a multicomponent mixture for the quality control of traditional Chinese medicine injections with the example of Danhong injection (DHI). The standardized chemical profile of DHI has been established based on liquid chromatography with diode array detection. High-performance liquid chromatography coupled with time-of-flight mass spectrometry and high-performance liquid chromatography with electrospray multistage tandem ion-trap mass spectrometry have been developed to identify the major constituents in DHI. The structures of 26 compounds including nucleotides, phenolic acids, and flavonoid glycosides were identified or tentatively characterized. Meanwhile, the simultaneous determination of seven marker constituents, including uridine, adenosine, danshensu, protocatechuic aldehyde, p-coumaric acid, rosmarinic acid, and salvianolic acid B, in DHI was performed by multiwavelength detection based on high-performance liquid chromatography with diode array detection. The integrated qualitative and quantitative characterization strategy provided an effective and reliable pattern for the comprehensive and systematic characterization of the complex traditional Chinese medicine system. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Application of characteristic ion filtering with ultra-high performance liquid chromatography quadrupole time of flight tandem mass spectrometry for rapid detection and identification of chemical profiling in Eucommia ulmoides Oliv.

    PubMed

    He, Mingzhen; Jia, Jia; Li, Junmao; Wu, Bei; Huang, Wenping; Liu, Mi; Li, Yan; Yang, Shilin; Ouyang, Hui; Feng, Yulin

    2018-06-15

    Efficient targeted identification of chemical constituents from traditional Chinese medicine is still a major challenge. In this study, we used a characteristic ion filtering strategy to characterize compounds of Eucommia ulmoides Oliv. by ultra-high performance liquid chromatography quadrupole time of flight tandem mass spectrometry (UHPLC-ESI-Q-TOF-MS/MS). By using the ion filtering approach, target constituents of Eucommia ulmoides Oliv. were easily tentatively identified from the enormous LC/MS data set. The strategy consisted of the following three steps: 1) To establishing a characteristic ion database by diagnostic product ions or neutral loss fragments; 2) To evaluate the structural information of the compounds by high-resolution diagnostic characteristic ion filtering; 3) To confirm the different classes by chemical profiling according to their MS/MS spectra. In this study, characteristic ions are summarized as five major groups of compounds in Eucommia ulmoides Oliv. In total, 113 compounds were tentatively identified, including 23 potentially novel compounds. The results form a foundation for the quality control and chemical basis of Eucommia ulmoides Oliv. Copyright © 2018 Elsevier B.V. All rights reserved.

  15. Determination of benzothiazole and benzotriazole derivates in tire and clothing textile samples by high performance liquid chromatography-electrospray ionization tandem mass spectrometry.

    PubMed

    Avagyan, Rozanna; Sadiktsis, Ioannis; Thorsén, Gunnar; Östman, Conny; Westerholm, Roger

    2013-09-13

    A high performance liquid chromatography-tandem mass spectrometry method utilizing electrospray ionization in positive and negative mode has been developed for the separation and detection of benzothiazole and benzotriazole derivates. Ultra-sonication assisted solvent extraction of these compounds has also been developed and the overall method demonstrated on a selected clothing textile and an automobile tire sample. Matrix effects and extraction recoveries, as well as linearity and limits of detection have been evaluated. The calibration curves spanned over more than two orders of magnitude with coefficients of correlation R(2)>0.99 and the limits of detection and the limits of quantification were in the range 1.7-58pg injected and 18-140pg/g, respectively. The extraction recoveries ranged between 69% and 102% and the matrix effects between 75% and 101%. Benzothiazole and benzotriazole derivates were determined in the textile sample and benzothiazole derivatives determined in the tire sample with good analytical performance. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Tunnel frit: a nonmetallic in-capillary frit for nanoflow ultra high-performance liquid chromatography-mass spectrometryapplications.

    PubMed

    Chen, Chao-Jung; Chen, Wei-Yun; Tseng, Mei-Chun; Chen, Yet-Ran

    2012-01-03

    In this study, an easy method to fabricate a durable in-capillary frit was developed for use in nanoflow liquid chromatography (nanoLC). A small orifice was tunneled into the sol-gel frit during the polymerization process resulting in the simple fabrication of a tunnel frit. A short packing tunnel frit column (2 cm, C(18) particles) was able to sustain over 10,000 psi continuous liquid flow for 10 days without observation of particle loss, and back pressure variation was less than 5%. The tunnel frit was successfully applied to the fabrication of nanoflow ultra high-performance liquid chromatography (nano-UHPLC) trap and analytical columns. In the analysis of tryptic peptides, the tunnel frit trap and analytical columns were demonstrated to have high separation efficiency and sensitivity. In analysis of phosphopeptides, the use of the nonmetallic tunnel frit column showed better sensitivity than the metallic frit column. This design can facilitate the preparation of nano-HPLC and nano-UHPLC columns and the packing material can easily be refilled when the column is severely contaminated or clogged. © 2011 American Chemical Society

  17. Simultaneous enantioselective determination of phenylpyrazole insecticide flufiprole and its chiral metabolite in paddy field ecosystem by ultra-high performance liquid chromatography/tandem mass spectrometry.

    PubMed

    Li, Jing; Zhang, Yuting; Cheng, Youpu; Yuan, Shankui; Liu, Lei; Shao, Hui; Li, Hui; Li, Na; Zhao, Pengyue; Guo, Yongze

    2016-03-20

    A novel and sensitive ultra-high performance liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method was developed and validated for simultaneous enantioselective determination of flufiprole and its hydrolysis metabolite in paddy field ecosystem. The separation and determination were performed using reversed-phase chromatography on a novel cellulose chiral stationary phase, a Lux Cellulose-4 (150 mm × 2.0 mm) column, under isocratic conditions at 0.25 mL/min flow rate. The effects of other four different polysaccharide-based chiral stationary phases (CSPs) on the separation and simultaneous enantioseparation of the two target compounds were also evaluated. The elution orders of the eluting enantiomers were identified by an optical rotation detector. Modified QuEChERS (acronym for Quick, Easy, Cheap, Effective, Rugged and Safe) method and solid-phase extraction (SPE) were used for the enrichment and cleanup of paddy water, rice straw, brown rice and paddy soil samples, respectively. Parameters including the matrix effect, linearity, precision, accuracy and stability were evaluated. Under the optimal conditions, the mean recoveries for all enantiomers from the above four sample matrix were ranged from 83.6% to 107%, with relative standard deviations (RSD) in the range of 1.0-5.8%. Coefficients of determination R(2)≥0.998 were achieved for each enantiomer in paddy water, rice straw, brown rice and paddy soil matrix calibration curves within the range of 5-500 μg/kg. The limits of quantification (LOQ) for all stereoisomers in the above four matrices were all below 2.0 μg/kg. The methodology was successfully applied for simultaneously enantioselective analysis of flufiprole enantiomers and their chiral metabolite in the real samples, indicating its efficacy in investigating the environmental stereochemistry of flufiprole in paddy field ecosystem. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Development and validation of a ultra high performance liquid chromatography-tandem mass spectrometric method for the direct detection of formoterol in human urine.

    PubMed

    Sardela, V F; Deventer, K; Pereira, H M G; de Aquino Neto, F R; Van Eenoo, P

    2012-11-01

    Formoterol is a long acting β(2)-agonist and has proven to be a very effective bronchodilating agent. Hence it is frequently applied therapeutically for the treatment of asthma. Because β(2)-agonists might be misused in sports for the stimulatory effects and for growth-promoting action their use is restricted. Since January 2012, formoterol is prohibited in urinary concentrations higher than 30 ng/mL. The objective of this study was to develop and validate a simple and robust ultra high performance liquid chromatographic-tandem mass spectrometric (UHPLC-MS/MS) method for the direct quantification of formoterol in urine. Sample preparation was limited to an enzymatic hydrolysis step after which 2 μL was injected in the chromatographic system. Chromatography was performed on a C(8)-column using gradient conditions. The mobile phase consisted of water/methanol (H(2)O/MeOH) both containing 0.1% acetic acid (HOAc) and 1mM ammonium acetate (NH(4)OAc). Calibration curve were constructed between 15 and 60 ng/mL. Validation data showed bias of 1.3% and imprecision of 5.4% at the threshold. Ion suppression/enhancement never exceeded 7%. Calculating measurement uncertainty showed proof of applicability of the method. Stability of formoterol was also investigated at 56 °C (accelerated stability test) at pH 1.0/5.2/7.0 and 9.5. At the physiological pH values of 5.2 and 7.0, formoterol showed good stability. At pH 1.0 and 9.5 significant degradation was observed. Copyright © 2012 Elsevier B.V. All rights reserved.

  19. Simultaneous determination of chlorantraniliprole and cyantraniliprole in fruits, vegetables and cereals using ultra-high-performance liquid chromatography-tandem mass spectrometry with the isotope-labelled internal standard method.

    PubMed

    Pan, Xinglu; Dong, Fengshou; Xu, Jun; Liu, Xingang; Chen, Zenglong; Liu, Na; Chen, Xixi; Tao, Yan; Zhang, Hongjun; Zheng, Yongquan

    2015-05-01

    A reliable and sensitive isotope-labelled internal standard method for simultaneous determination of chlorantraniliprole and cyantraniliprole in fruits (apple and grape), vegetables (cucumber and tomato) and cereals (rice and wheat) using ultra-high-performance liquid chromatography-tandem mass spectrometry was developed. Isotope-labelled internal standards were effective in compensating for the loss in the pretreatment and overcoming the matrix effect. The analytes were extracted with acetonitrile and cleaned up with different kinds of sorbents. The determination of the target compounds was achieved in less than 4 min using a T3 column combined with an electrospray ionization source in positive mode. The overall average relative recoveries in all matrices at three spiking levels (10, 20 and 50 μg kg(-1)) ranged from 95.5 to 106.2 %, with all relative standard deviations being less than 14.4 % for all analytes. The limits of detection did not exceed 0.085 μg kg(-1) and the limits of quantification were below 0.28 μg kg(-1) in all matrices. The method was demonstrated to be convenient and accurate for the routine monitoring of chlorantraniliprole and cyantraniliprole in fruits, vegetables and cereals.

  20. Simultaneous Determination of Underivatized Vitamin B1 and B6 in Whole Blood by Reversed Phase Ultra High Performance Liquid Chromatography Tandem Mass Spectrometry

    PubMed Central

    Puts, Johan; de Groot, Monique; Haex, Martin; Jakobs, Bernadette

    2015-01-01

    Background Vitamin B1 (thiamine-diphosphate) and B6 (pyridoxal-5’phosphate) are micronutrients. Analysis of these micronutrients is important to diagnose potential deficiency which often occurs in elderly people due to malnutrition, in severe alcoholism and in gastrointestinal compromise due to bypass surgery or disease. Existing High Performance Liquid Chromatography (HPLC) based methods include the need for derivatization and long analysis time. We developed an Ultra High Performance Liquid Chromatography Tandem Mass spectrometry (UHPLC-MS/MS) assay with internal standards for simultaneous measurement of underivatized thiamine-diphosphate and pyridoxal-5’phosphate without use of ion pairing reagent. Methods Whole blood, deproteinized with perchloric acid, containing deuterium labelled internal standards thiamine-diphosphate(thiazole-methyl-D3) and pyridoxal-5’phosphate(methyl-D3), was analyzed by UHPLC-MS/MS. The method was validated for imprecision, linearity, recovery and limit of quantification. Alternate (quantitative) method comparisons of the new versus currently used routine HPLC methods were established with Deming regression. Results Thiamine-diphosphate and pyridoxal-5’phosphate were measured within 2.5 minutes instrumental run time. Limits of detection were 2.8 nmol/L and 7.8 nmol/L for thiamine-diphosphate and pyridoxal-5’phosphate respectively. Limit of quantification was 9.4 nmol/L for thiamine-diphosphate and 25.9 nmol/L for pyridoxal-5’phosphate. The total imprecision ranged from 3.5–7.7% for thiamine-diphosphate (44–157 nmol/L) and 6.0–10.4% for pyridoxal-5’phosphate (30–130 nmol/L). Extraction recoveries were 101–102% ± 2.5% (thiamine-diphosphate) and 98–100% ± 5% (pyridoxal-5’phosphate). Deming regression yielded slopes of 0.926 and 0.990 in patient samples (n = 282) and national proficiency testing samples (n = 12) respectively, intercepts of +3.5 and +3 for thiamine-diphosphate (n = 282 and n = 12) and slopes of

  1. Multiresidue analysis of endocrine-disrupting compounds and perfluorinated sulfates and carboxylic acids in sediments by ultra-high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Cavaliere, Chiara; Capriotti, Anna Laura; Ferraris, Francesca; Foglia, Patrizia; Samperi, Roberto; Ventura, Salvatore; Laganà, Aldo

    2016-03-18

    A multiresidue analytical method for the determination of 11 perfluorinated compounds and 22 endocrine-disrupting compounds (ECDs) including 13 natural and synthetic estrogens (free and conjugated forms), 2 alkylphenols, 1 plasticiser, 2 UV-filters, 1 antimicrobial, and 2 organophosphorus compounds in sediments has been developed. Ultrasound-assisted extraction followed by solid phase extraction (SPE) with graphitized carbon black (GCB) cartridge as clean-up step were used. The extraction process yield was optimized in terms of solvent composition. Then, a 3(2) experimental design was used to optimize solvent volume and sonication time by response surface methodology, which simplifies the optimization procedure. The final extract was analyzed by ultra-high performance liquid chromatography coupled with tandem mass spectrometry. The optimized sample preparation method is simple and robust, and allows recovery of ECDs belonging to different classes in a complex matrix such as sediment. The use of GCB for SPE allowed to obtain with a single clean-up procedure excellent recoveries ranging between 75 and 110% (relative standard deviation <16%). The developed methodology has been successfully applied to the analysis of ECDs in sediments from different rivers and lakes of the Lazio Region (Italy). These analyses have shown the ubiquitous presence of chloro-substituted organophosphorus flame retardants and bisphenol A, while other analyzed compounds were occasionally found at concentration between the limit of detection and quantification. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. High-throughput, Highly Sensitive Analyses of Bacterial Morphogenesis Using Ultra Performance Liquid Chromatography*

    PubMed Central

    Desmarais, Samantha M.; Tropini, Carolina; Miguel, Amanda; Cava, Felipe; Monds, Russell D.; de Pedro, Miguel A.; Huang, Kerwyn Casey

    2015-01-01

    The bacterial cell wall is a network of glycan strands cross-linked by short peptides (peptidoglycan); it is responsible for the mechanical integrity of the cell and shape determination. Liquid chromatography can be used to measure the abundance of the muropeptide subunits composing the cell wall. Characteristics such as the degree of cross-linking and average glycan strand length are known to vary across species. However, a systematic comparison among strains of a given species has yet to be undertaken, making it difficult to assess the origins of variability in peptidoglycan composition. We present a protocol for muropeptide analysis using ultra performance liquid chromatography (UPLC) and demonstrate that UPLC achieves resolution comparable with that of HPLC while requiring orders of magnitude less injection volume and a fraction of the elution time. We also developed a software platform to automate the identification and quantification of chromatographic peaks, which we demonstrate has improved accuracy relative to other software. This combined experimental and computational methodology revealed that peptidoglycan composition was approximately maintained across strains from three Gram-negative species despite taxonomical and morphological differences. Peptidoglycan composition and density were maintained after we systematically altered cell size in Escherichia coli using the antibiotic A22, indicating that cell shape is largely decoupled from the biochemistry of peptidoglycan synthesis. High-throughput, sensitive UPLC combined with our automated software for chromatographic analysis will accelerate the discovery of peptidoglycan composition and the molecular mechanisms of cell wall structure determination. PMID:26468288

  3. Determination of colistin in animal tissues, egg, milk, and feed by ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Fu, Qin; Li, Xiaowei; Zheng, Kangni; Ke, Yuebin; Wang, Yingyu; Wang, Lina; Yu, Fugen; Xia, Xi

    2018-05-15

    A confirmatory method for the determination of colistin in animal tissues, egg, milk, and feed was developed and validated. Colistin A and colistin B were extracted from samples with the mixture of 10% trichloroacetic acid-acetonitrile and isolated with mixed-mode weak cation exchange cartridge. Analytes were separated from matrix components using ultra-high performance liquid chromatography, and detected with electrospray ionization on a triple quadrupole mass spectrometer. Mean recoveries ranged from 78.0% to 115.6% with intra-day and inter-day relative standard deviation lower than 8.4% and 12.4%, respectively. The quantitation limits for different matrices were between 5 and 30 μg/kg, which was satisfactory for surveillance monitoring. The developed method was applied to the analysis of real samples collected from different provinces of China, and 19 out of 348 samples were found to be contaminated, with the highest concentration of approximately 12,000 μg/kg colistin A and 10,000 μg/kg colistin B in feed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Ultra-Trace Analysis of Nine Macrolides, including Tulathromycin A (Draxxin), in Edible Animal Tissues with Mini-Column Liquid Chromatography Tandem Mass Spectrometry

    USDA-ARS?s Scientific Manuscript database

    Analysis of 9 macrolides is presented, including tulathromycin A (Draxxin), in beef, poultry and pork muscle with a simple multi-residue extraction and analysis method using high performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. The extraction method inv...

  5. Screening antiallergic components from Carthamus tinctorius using rat basophilic leukemia 2H3 cell membrane chromatography combined with high-performance liquid chromatography and tandem mass spectrometry.

    PubMed

    Han, Shengli; Huang, Jing; Cui, Ronghua; Zhang, Tao

    2015-02-01

    Carthamus tinctorius, used in traditional Chinese medicine, has many pharmacological effects, such as anticoagulant effects, antioxidant effects, antiaging effects, regulation of gene expression, and antitumor effects. However, there is no report on the antiallergic effects of the components in C. tinctorius. In the present study, we investigated the antiallergic components of C. tinctorius and its mechanism of action. A rat basophilic leukemia 2H3/cell membrane chromatography coupled online with high-performance liquid chromatography and tandem mass spectrometry method was developed to screen antiallergic components from C. tinctorius. The screening results showed that Hydroxysafflor yellow A, from C. tinctorius, was the targeted component that retained on the rat basophilic leukemia 2H3/cell membrane chromatography column. We measured the amount of β-hexosaminidase and histamine released in mast cells and the key markers of degranulation. The release assays showed that Hydroxysafflor yellow A could attenuate the immunoglobulin E induced release of allergic cytokines without affecting cell viability from 1.0 to 50.0 μM. In conclusion, the established rat basophilic leukemia 2H3 cell membrane chromatography coupled with online high-performance liquid chromatography and tandem mass spectrometry method successfully screened and identified Hydroxysafflor yellow A from C. tinctorius as a potential antiallergic component. Pharmacological analysis elucidated that Hydroxysafflor yellow A is an effective natural component for inhibiting immunoglobulin E-antigen-mediated degranulation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Analysis of major antioxidants from extracts of Myrmecodia pendans by UV/visible spectrophotometer, liquid chromatography/tandem mass spectrometry, and high-performance liquid chromatography/UV techniques.

    PubMed

    Engida, Adam Mekonnen; Faika, Sitti; Nguyen-Thi, Bich Thuyen; Ju, Yi-Hsu

    2015-06-01

    In the present work, heat reflux extraction with ethanol/water (80:20; v/v) as the solvent was used to extract antioxidants from Myrmecodia pendans. The crude extract (CE) was fractionated using hexane and ethyl acetate. Ethyl acetate fraction (EAF) and aqueous fraction were collected. Antioxidant activity against 1,1-diphenyl-2-picrylhydrazyl-radical radical and ferric reducing power of the CE, EAF, and aqueous fraction were evaluated. EAF showed comparable antioxidant activity against 1,1-diphenyl-2-picrylhydrazyl-radical radical and ferric reducing power to those of the CE. UV/visible, liquid chromatography/electrospray ionization/tandem mass spectrometry, and high-performance liquid chromatography were employed for identifying the major antioxidant compounds in the EAF. Three major phenolic compounds (rosmarinic acid, procyanidin B1, and polymer of procyanidin B1) were identified. The first two compounds were confirmed and quantified by high-performance liquid chromatography using authentic standards, but confirmation of the third compound was hampered by a lack of commercial standard. Concentrations of rosmarinic acid and procyanidin B1 in the EAF were found to be 20.688 ± 1.573 mg/g dry sample and 3.236 ± 0.280 mg/g dry sample, respectively. All these three compounds are reported for the first time in sarang semut. Copyright © 2014. Published by Elsevier B.V.

  7. Analytical interference of 4-hydroxy-3-methoxymethamphetamine with the measurement of plasma free normetanephrine by ultra-high pressure liquid chromatography-tandem mass spectrometry.

    PubMed

    Dunand, Marielle; Donzelli, Massimiliano; Rickli, Anna; Hysek, Cédric M; Liechti, Matthias E; Grouzmann, Eric

    2014-08-01

    The diagnosis of pheochromocytoma relies on the measurement of plasma free metanephrines assay whose reliability has been considerably improved by ultra-high pressure liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Here we report an analytical interference occurring between 4-hydroxy-3-methoxymethamphetamine (HMMA), a metabolite of 3,4-methylenedioxymethamphetamine (MDMA, "Ecstasy"), and normetanephrine (NMN) since they share a common pharmacophore resulting in the same product ion after fragmentation. Synthetic HMMA was spiked into plasma samples containing various concentrations of NMN and the intensity of the interference was determined by UPLC-MS/MS before and after improvement of the analytical method. Using a careful adjustment of chromatographic conditions including the change of the UPLC analytical column, we were able to distinguish both compounds. HMMA interference for NMN determination should be seriously considered since MDMA activates the sympathetic nervous system and if confounded with NMN may lead to false-positive tests when performing a differential diagnostic of pheochromocytoma. Copyright © 2014 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

  8. Determination of rutin in rat plasma by ultra performance liquid chromatography tandem mass spectrometry and application to pharmacokinetic study.

    PubMed

    Chen, Mengchun; Zhang, Xiaoqian; Wang, Hao; Lin, Baoli; Wang, Shuanghu; Hu, Guoxin

    2015-04-01

    A sensitive and rapid ultra performance liquid chromatography tandem mass spectrometry (UPLC-MS-MS) method for the determination of rutin in rat plasma was developed and validated. After addition of tolbutamide as internal standard (IS), protein precipitation by acetonitrile was used as sample preparation. The chromatographic separation was performed on an Acquity UPLC BEH C18 column (2.1 × 50 mm, 1.7 μm particle size), using acetonitrile-0.1% formic acid as the mobile phase with gradient elution, delivered at a flow-rate of 0.4 mL/min. Mass spectrometric analysis was performed using a XEVO TQD mass spectrometer coupled with an electro-spray ionization (ESI) source in the positive ion mode. The MRM transitions of m/z 610.91→302.98 and m/z 271.2→155.1 were used to quantify for rutin and tolbutamide, respectively. This assay method has been fully validated in terms of specificity, linearity, recovery and matrix effect, accuracy, precision and stability. Calibration curves were linear in the concentration ranges of 25-2000 ng/mL for rutin. Only 3 min was needed for an analytical run. This developed method was successfully used for determination of rutin in rat plasma for pharmacokinetic study. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  9. Simultaneous quantification of neuroactive dopamine serotonin and kynurenine pathway metabolites in gender-specific youth urine by ultra performance liquid chromatography tandem high resolution mass spectrometry.

    PubMed

    Lu, Haihua; Yu, Jing; Wang, Jun; Wu, Linlin; Xiao, Hang; Gao, Rong

    2016-04-15

    Neuroactive metabolites in dopamine, serotonin and kynurenine metabolic pathways play key roles in several physiological processes and their imbalances have been implicated in the pathophysiology of a wide range of disorders. The association of these metabolites' alterations with various pathologies has raised interest in analytical methods for accurate quantification in biological fluids. However, simultaneous measurement of various neuroactive metabolites represents great challenges due to their trace level, high polarity and instability. In this study, an analytical method was developed and validated for accurately quantifying 12 neuroactive metabolites covering three metabolic pathways in youth urine by ultra performance liquid chromatography coupled to electrospray tandem high resolution mass spectrometry (UPLC-ESI-HRMS/MS). The strategy of dansyl chloride derivatization followed by solid phase extraction on C18 cartridges were employed to reduce matrix interference and improve the extraction efficiency. The reverse phase chromatographic separation was achieved with a gradient elution program in 20 min. The high resolution mass spectrometer (Q Exactive) was employed, with confirmation and quantification by Target-MS/MS scan mode. Youth urine samples collected from 100 healthy volunteers (Female:Male=1:1) were analyzed to explore the differences in metabolite profile and their turnover between genders. The results demonstrated that the UPLC-ESI-HRMS/MS method is sensitive and robust, suitable for monitoring a large panel of metabolites and for discovering new biomarkers in the medical fields. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Enantiomeric separation and quantification of R/S-amphetamine in urine by ultra-high performance supercritical fluid chromatography tandem mass spectrometry.

    PubMed

    Hegstad, S; Havnen, H; Helland, A; Spigset, O; Frost, J

    2018-03-01

    To distinguish between legal and illegal consumption of amphetamine reliable analytical methods for chiral separation of the R- and S-enantiomers of amphetamine in biological specimens are required. In this regard, supercritical fluid chromatography (SFC) has several potential advantages over liquid chromatography, including rapid separation of enantiomers due to low viscosity and high diffusivity of supercritical carbon dioxide, the main component in the SFC mobile phase. A method for enantiomeric separation and quantification of R- and S-amphetamine in urine was developed and validated using ultra-high performance supercritical fluid chromatography-tandem mass spectrometry (UHPSFC-MS/MS). Sample preparation prior to UHPSFC-MS/MS analysis was a semi-automatic solid phase extraction method. The UHPSFC-MS/MS method used a Chiralpak AD-3 column with a mobile phase consisting of CO 2 and 0.2% cyclohexylamine in 2-propanol. The injection volume was 2 μL and run-time was 6 min. MS/MS detection was performed with positive electrospray ionization and two multiple reaction monitoring transitions (m/z 136.1 > 119.0 and m/z 136.1 > 91.0). The calibration range was 50-10,000 ng/mL for each enantiomer. The between-assay relative standard deviations were in the range of 3.7-7.6%. Recovery was 92-93% and matrix effects ranged from 100 to 104% corrected with internal standard. After development and validation, the method has been successfully implemented in routine use at our laboratory for both separation and quantification of R/S-amphetamine, and has proved to be a reliable and useful tool for distinguishing intake of R- and S-amphetamine in authentic patient samples. Copyright © 2018 Elsevier B.V. All rights reserved.

  11. Determination of 2-alkylcyclobutanones by combining precolumn derivatization with 1-naphthalenyl hydrazine and ultra-performance liquid chromatography with fluorescence detection.

    PubMed

    Meng, Xiangpeng; Tong, Tong; Wang, Lianrong; Liu, Hanxia; Chan, Wan

    2016-05-01

    2-Alkylcyclobutanones (2-ACBs) are uniquely formed when triglycerides-containing food products are exposed to ionizing radiation. Thus, 2-ACBs have been used as marker molecules to identify irradiated food. Most methods to determine 2-ACBs involve mass spectrometric detection after chromatographic separation. The spectrofluorometer is rarely used to determine 2-ACBs because these molecules do not fluoresce. In this study, we developed an ultra-performance liquid chromatography (UPLC) method to determine 2-ACBs. 2-ACBs were converted into fluorophores after reacting with 1-naphthalenyl hydrazine to facilitate their sensitive and selective detection using a fluorescence detector (FLD). Analysis of 2-ACBs using our developed UPLC-FLD method allows sensitive determination of 2-ACBs at a detection limit of 2 ng 2-ACBs per g of fat (30 pg/injection), which is significantly lower than that of existing analytical methods. After validation for trueness and precision, the method was applied to γ-irradiated chicken samples to determine their 2-ACB content. Comparative studies employing liquid chromatography-tandem mass spectrometric method revealed no systematic difference between the two methods, thereby demonstrating that the proposed UPLC-FLD method can be suitably used to determine 2-ACBs in irradiated foodstuffs. Graphical Abstract Determination of radiation-induced food-borne 2-dodecylcyclobutanone and 2-tetradecylcyclobutanone by combining 1-naphthalenyl hydrazine derivatization and ultra-performance liquid chromatography with fluorescence detection.

  12. Simultaneous determination of tilianin and its metabolites in mice using ultra-high-performance liquid chromatography with tandem mass spectrometry and its application to a pharmacokinetic study.

    PubMed

    Wang, Liping; Chen, Qingwei; Zhu, Lijun; Zeng, Xuejun; Li, Qiang; Hu, Ming; Wang, Xinchun; Liu, Zhongqiu

    2018-04-01

    Tilianin is an active flavonoid glycoside found in many medical plants. Data are lacking regarding its pharmacokinetics and disposition in vivo. The objective of this study was to develop a sensitive, reliable and validated ultra-high-performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS) method to simultaneously quantify tilianin and its main metabolites and to determine its pharmacokinetics in wild-type and breast cancer resistance protein knockout (Bcrp1-/-) FVB mice. Chromatographic separation was accomplished on a C 18 column by utilizing acetonitrile and 0.5 mm ammonium acetate as the mobile phase. Mass spectrometric detection was performed using electrospray ionization in both positive and negative modes. The results showed that the precision, accuracy and recovery, as well as the stability of tilianin and its metabolites in mouse plasma, were all within acceptable limits. Acacetin-7-glucuronide and acacetin-7-sulfate were the major metabolites of tilianin in mouse plasma. Moreover, systemic exposure of acacetin-7-sulfate was significantly higher in Bcrp1 (-/-) FVB mice compared with wild-type FVB mice. In conclusion, the fully validated UHPLC-MS/MS method was sensitive, reliable, and was successfully applied to assess the pharmacokinetics of tilianin in wild-type and Bcrp1 (-/-) FVB mice. Breast cancer resistance protein had a significant impact on the elimination of the sulfated metabolite of tilianin in vivo. Copyright © 2017 John Wiley & Sons, Ltd.

  13. Sensitivity enhancement by chromatographic peak concentration with ultra-high performance liquid chromatography-nuclear magnetic resonance spectroscopy for minor impurity analysis.

    PubMed

    Tokunaga, Takashi; Akagi, Ken-Ichi; Okamoto, Masahiko

    2017-07-28

    High performance liquid chromatography can be coupled with nuclear magnetic resonance (NMR) spectroscopy to give a powerful analytical method known as liquid chromatography-nuclear magnetic resonance (LC-NMR) spectroscopy, which can be used to determine the chemical structures of the components of complex mixtures. However, intrinsic limitations in the sensitivity of NMR spectroscopy have restricted the scope of this procedure, and resolving these limitations remains a critical problem for analysis. In this study, we coupled ultra-high performance liquid chromatography (UHPLC) with NMR to give a simple and versatile analytical method with higher sensitivity than conventional LC-NMR. UHPLC separation enabled the concentration of individual peaks to give a volume similar to that of the NMR flow cell, thereby maximizing the sensitivity to the theoretical upper limit. The UHPLC concentration of compound peaks present at typical impurity levels (5.0-13.1 nmol) in a mixture led to at most three-fold increase in the signal-to-noise ratio compared with LC-NMR. Furthermore, we demonstrated the use of UHPLC-NMR for obtaining structural information of a minor impurity in a reaction mixture in actual laboratory-scale development of a synthetic process. Using UHPLC-NMR, the experimental run times for chromatography and NMR were greatly reduced compared with LC-NMR. UHPLC-NMR successfully overcomes the difficulties associated with analyses of minor components in a complex mixture by LC-NMR, which are problematic even when an ultra-high field magnet and cryogenic probe are used. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Use of experimental design in the investigation of stir bar sorptive extraction followed by ultra-high-performance liquid chromatography-tandem mass spectrometry for the analysis of explosives in water samples.

    PubMed

    Schramm, Sébastien; Vailhen, Dominique; Bridoux, Maxime Cyril

    2016-02-12

    A method for the sensitive quantification of trace amounts of organic explosives in water samples was developed by using stir bar sorptive extraction (SBSE) followed by liquid desorption and ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The proposed method was developed and optimized using a statistical design of experiment approach. Use of experimental designs allowed a complete study of 10 factors and 8 analytes including nitro-aromatics, amino-nitro-aromatics and nitric esters. The liquid desorption study was performed using a full factorial experimental design followed by a kinetic study. Four different variables were tested here: the liquid desorption mode (stirring or sonication), the chemical nature of the stir bar (PDMS or PDMS-PEG), the composition of the liquid desorption phase and finally, the volume of solvent used for the liquid desorption. On the other hand, the SBSE extraction study was performed using a Doehlert design. SBSE extraction conditions such as extraction time profiles, sample volume, modifier addition, and acetic acid addition were examined. After optimization of the experimental parameters, sensitivity was improved by a factor 5-30, depending on the compound studied, due to the enrichment factors reached using the SBSE method. Limits of detection were in the ng/L level for all analytes studied. Reproducibility of the extraction with different stir bars was close to the reproducibility of the analytical method (RSD between 4 and 16%). Extractions in various water sample matrices (spring, mineral and underground water) have shown similar enrichment compared to ultrapure water, revealing very low matrix effects. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. [Determination of 27 industrial dyes in juice and wine using ultra performance liquid chromatography with electrospray ionization tandem quadrupole mass spectrometry].

    PubMed

    Zhao, Shan; Zhang, Jing; Yang, Yi; Shao, Bing

    2010-04-01

    A method for the determination of 27 industrial dyes in juice and wine has been developed using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/ MS). Acetonitrile was used as extraction solvent, and sodium chloride was added to salt out the analytes from the samples. Chromatographic separation was performed on a C18 column with the gradient elution and the mass spectrometric acquisition was carried out under the mode of multiple reaction monitoring (MRM). Twenty-four of the 27 dyes were detected under positive ionization mode using the mobile phase of acetonitrile and water containing 0.1% formic acid. The other 3 dyes were analyzed under negative ionization mode with the mobile phase of acetonitrile and water. As a result, the average recoveries of 27 dyes spiked in juice ranged from 57.0% to 117.7% with the relative standard deviations (RSDs) of 2.4%-17.7%, and the average recoveries of 27 dyes spiked in wine ranged from 40.8% to 109.4% with the RSDs of 1.6%-17.9%. The limits of quantification (LOQs) of 27 dyes spiked in juice were in the range of 0.1-50 microg/kg, and 0.2-50 microg/kg for those spiked in wine. This method can be applied to rapid detection of illegally added dyes in soft drinks due to its simplicity and high sensitivity.

  16. Quantification of 31 illicit and medicinal drugs and metabolites in whole blood by fully automated solid-phase extraction and ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Bjørk, Marie Kjærgaard; Simonsen, Kirsten Wiese; Andersen, David Wederkinck; Dalsgaard, Petur Weihe; Sigurðardóttir, Stella Rögn; Linnet, Kristian; Rasmussen, Brian Schou

    2013-03-01

    An efficient method for analyzing illegal and medicinal drugs in whole blood using fully automated sample preparation and short ultra-high-performance liquid chromatography-tandem mass spectrometry (MS/MS) run time is presented. A selection of 31 drugs, including amphetamines, cocaine, opioids, and benzodiazepines, was used. In order to increase the efficiency of routine analysis, a robotic system based on automated liquid handling and capable of handling all unit operation for sample preparation was built on a Freedom Evo 200 platform with several add-ons from Tecan and third-party vendors. Solid-phase extraction was performed using Strata X-C plates. Extraction time for 96 samples was less than 3 h. Chromatography was performed using an ACQUITY UPLC system (Waters Corporation, Milford, USA). Analytes were separated on a 100 mm × 2.1 mm, 1.7 μm Acquity UPLC CSH C(18) column using a 6.5 min 0.1 % ammonia (25 %) in water/0.1 % ammonia (25 %) in methanol gradient and quantified by MS/MS (Waters Quattro Premier XE) in multiple-reaction monitoring mode. Full validation, including linearity, precision and trueness, matrix effect, ion suppression/enhancement of co-eluting analytes, recovery, and specificity, was performed. The method was employed successfully in the laboratory and used for routine analysis of forensic material. In combination with tetrahydrocannabinol analysis, the method covered 96 % of cases involving driving under the influence of drugs. The manual labor involved in preparing blood samples, solvents, etc., was reduced to a half an hour per batch. The automated sample preparation setup also minimized human exposure to hazardous materials, provided highly improved ergonomics, and eliminated manual pipetting.

  17. Comprehensive quantitative analysis of Chinese patent drug YinHuang drop pill by ultra high-performance liquid chromatography quadrupole time of flight mass spectrometry.

    PubMed

    Wong, Tin-Long; An, Ya-Qi; Yan, Bing-Chao; Yue, Rui-Qi; Zhang, Tian-Bo; Ho, Hing-Man; Ren, Tian-Jing; Fung, Hau-Yee; Ma, Dik-Lung; Leung, Chung-Hang; Liu, Zhong-Liang; Pu, Jian-Xin; Han, Quan-Bin; Sun, Han-Dong

    2016-06-05

    YinHuang drop pill (YHDP) is a new preparation, derived from the traditional YinHuang (YH) decoction. Since drop pills are one of the newly developed forms of Chinese patent drugs, not much research has been done regarding the quality and efficacy. This study aims to establish a comprehensive quantitative analysis of the chemical profile of YHDP. ultra high-performance liquid chromatography quadrupole time of flight mass spectrometry (UHPLC-Q-TOF-MS/MS) was used to identify 34 non-sugar small molecules including 15 flavonoids, 9 phenolic acids, 5 saponins, 1 iridoid, and 4 iridoid glycosides in YHDP samples, and 26 of them were quantitatively determined. Sugar composition of YHDP in terms of fructose, glucose and sucrose was examined via a high performance liquid chromatography-evaporative light scattering detector on an amide column (HPLC-NH2P-ELSD). Macromolecules were examined by high performance gel permeation chromatography coupled with ELSD (HPGPC-ELSD). The content of the drop pill's skeleton component PEG-4000 was also quantified via ultra-high performance liquid chromatography coupled with charged aerosol detector (UHPLC-CAD). The results showed that up to 73% (w/w) of YHDP could be quantitatively determined. Small molecules accounted for approximately 5%, PEG-4000 represented 68%, while no sugars or macromolecules were found. Furthermore, YHDP showed no significant differences in terms of daily dosage, compared to YinHuang granules and YinHuang oral liquid; however, it has a higher small molecules content compared to YinHuang lozenge. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. [Simultaneous determination of nine perfluorinated compound precursors in atmospheric precipitation by solid phase extraction and ultra performance liquid chromatography with tandem mass spectrometry].

    PubMed

    Zhang, Ming; Tang, Fangliang; Xu, Jianfen; Yu, Bo; Zhang, Wei; Yao, Jianliang; Hu, Minhua

    2017-10-08

    A high-throughput detection method has been developed for the determination of nine perfluorinated compound precursors (PFCPs) in atmospheric precipitation by solid phase extraction-ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (SPE-UPLC-ESI-MS/MS). The atmospheric precipitation samples were concentrated and purified with HLB solid phase extraction cartridges. The UPLC separation was performed on an HSS T 3 column (100 mm×2.1 mm, 1.7 μm) utilizing a gradient elution program of methanol and water as the mobile phases at a flow rate of 0.2 mL/min. The MS/MS detection was performed under negative electrospray ionization (ESI - ) in multiple reaction monitoring (MRM) mode. Good linearity was observed in the range of 0.05-5.00 μg/L, 0.50-50.0 μg/L or 5.00-500 μg/L with correlation coefficients from 0.9921 to 0.9995. The limits of detection (LODs) for the nine perfluorinated compound precursors were in the ranges of 0.05-7.9 ng/L. The recoveries ranged from 76.0% to 106% with the relative standard deviations between 0.72% and 13.7%. This method is characterized by high sensitivity and precision, extensive analytical range and quick analytical rate, and can be applied for the analysis of perfluorinated compound precursors in atmospheric precipitation.

  19. Determination of quinolone residues in infant and young children powdered milk combining solid-phase extraction and ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Herrera-Herrera, Antonio V; Hernández-Borges, Javier; Rodríguez-Delgado, Miguel A; Herrero, Miguel; Cifuentes, Alejandro

    2011-10-21

    The present work describes a method based on solid-phase extraction (SPE) and ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) for the simultaneous determination of three quinolones (pipemidic acid, oxolinic acid and flumequine) and twelve fluoroquinolones (marbofloxacin, fleroxacin, pefloxacin, levofloxacin, norfloxacin, ciprofloxacin, enrofloxacin, danofloxacin, lomefloxacin, difloxacin, sarafloxacin, and moxifloxacin) in different infant and young children powdered milks. After suitable deproteination of the reconstituted powdered samples, a SPE procedure was developed providing recovery values higher than 84% (RSDs lower than 13%) for all the analytes, with limits of detection between 0.04 and 0.52 μg/kg. UPLC-MS/MS analyses were carried out in less than 10 min. Sixteen infant and young children powdered milk samples of different origin, type and composition bought at Spanish markets were analyzed. Residues of the selected antibiotics were not detected in any of the analyzed samples. Copyright © 2011 Elsevier B.V. All rights reserved.

  20. Clonazepam quantification in human plasma by high-performance liquid chromatography coupled with electrospray tandem mass spectrometry in a bioequivalence study.

    PubMed

    Cavedal, Luiz E; Mendes, Fabiana D; Domingues, Claudia C; Patni, Anil K; Monif, Tausif; Reyar, Simrit; Pereira, Alberto Dos S; Mendes, Gustavo D; De Nucci, Gilberto

    2007-01-01

    A rapid, sensitive and specific method for quantifying clonazepam in human plasma using diazepam as the internal standard (IS) is described. The analyte and the IS were extracted from plasma by liquid-liquid extraction using a hexane/diethylether (20 : 80, v/v) solution. The extracts were analysed by high-performance liquid chromatography coupled with electrospray tandem mass spectrometry (HPLC-MS-MS). Chromatography was performed on a Jones Genesis C8 4 microm analytical column (100 x 2.1 mm i.d.). The method had a chromatographic run time of 3.0 min and a linear calibration curve over the range 0.5-50 ng/ml (r2 > 0.9965). The limit of quantification was 0.5 ng/ml. This HPLC/MS/MS procedure was used to assess the bioequivalence of two clonazepam 2 mg tablet formulations (clonazepam test formulation from Ranbaxy Laboratories Ltd and Rivotril from Roche Laboratórios Ltda as standard reference formulation). Copyright 2006 John Wiley & Sons, Ltd.

  1. Analysis of advanced glycation endproducts in selected food items by ultra-performance liquid chromatography tandem mass spectrometry: Presentation of a dietary AGE database.

    PubMed

    Scheijen, Jean L J M; Clevers, Egbert; Engelen, Lian; Dagnelie, Pieter C; Brouns, Fred; Stehouwer, Coen D A; Schalkwijk, Casper G

    2016-01-01

    The aim of this study was to validate an ultra-performance liquid chromatography tandem mass-spectrometry (UPLC-MS/MS) method for the determination of advanced glycation endproducts (AGEs) in food items and to analyze AGEs in a selection of food items commonly consumed in a Western diet. N(ε)-(carboxymethyl)lysine (CML), N(ε)-(1-carboxyethyl)lysine (CEL) and N(δ)-(5-hydro-5-methyl-4-imidazolon-2-yl)-ornithine (MG-H1) were quantified in the protein fractions of 190 food items using UPLC-MS/MS. Intra- and inter-day accuracy and precision were 2-29%. The calibration curves showed perfect linearity in water and food matrices. We found the highest AGE levels in high-heat processed nut or grain products, and canned meats. Fruits, vegetables, butter and coffee had the lowest AGE content. The described method proved to be suitable for the quantification of three major AGEs in food items. The presented dietary AGE database opens the possibility to further quantify actual dietary exposure to AGEs and to explore its physiological impact on human health. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. [Determination of triclosan and triclocarban in human breast milk by solid-phase extraction and ultra performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Zhang, Pin; Zhang, Jing; Shi, Ying; Shao, Bing

    2015-03-01

    An analytical method was developed to simultaneously detect triclosan (TCS) and triclocarban (TCC) in human breast milk using solid-phase extraction (SPE) with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Samples were extracted by acetonitrile and purified with C -18 SPE cartridge after enzymolysis with β-glucuronidase/arylsulfatase. The chromatographic separation was performed on a Waters ACQUITY UPLC™ HSS T3 column (100 mm x 2. 1 mm, 1. 8 µm) with gradient elution using methanol and water at a flow rate of 0. 3 ml/min. The target analytes were assayed by triple quadrupole mass spectrometer operating in the negative ion mode. Quantification was performed by isotopic internal standard calibration. Satisfactory linearity (r2 > 0. 999) was obtained over the range of 0. 2 - 20. 0 µg/L and 0. 02 - 2. 0 µg/L for triclosan and triclocarban, respectively, with the limits of quantifications (LOQs) of 0. 41 and 0. 03 µg/kg. Average recoveries of two target compounds (spiked at three concentration levels) ranged from 100. 2% to 119. 3%, with the relative standard deviations (RSDs) between 5. 91% and 11. 31% (n =6). Twenty-five real samples (n = 25) were detected containing TCS and TCC at concentrations of < LOQ - 0. 77 µg/kg and < LOQ - 4. 28 µg/kg, respectively. Due to its high sensitivity and good reproductivity, this method can be applied to analyze TCS and TCC in human breast milk.

  3. Rapid quantification of resveratrol in mouse plasma by ultra high pressure liquid chromatography (UPLC) coupled to tandem mass spectrometry.

    PubMed

    Castillo-Pichardo, Linette; Dharmawardhane, Suranganie; Rodríguez-Orengo, José F

    2014-12-01

    The objective of this study was to develop a rapid and sensitive method for the quantification of resveratrol, a polyphenolic compound with multiple health beneficial effects, in mouse plasma. We used reversed-phase ultra high pressure-liquid chromatography with tandem mass spectrometry detection for the determination of resveratrol levels in mouse plasma. An Agilent Zorbax Eclipse Plus C18 column (2.1 mm x 50 mm, 1.8 μm) was used as the stationary phase. The mobile phase consisted of a gradient formed using 1 mM ammonium fluoride and methanol. Using this improved method, we obtained a retention time of 2.2 min and a total run time of 5 min, for resveratrol. The calibration curve for resveratrol showed a linear range from 0.5 to 100 ng/mL. The average coefficient of variation was 6% for interday variation and 4% for intraday variation. The recovery for resveratrol in mouse plasma was 85 ± 10% (mean ± standard deviation). The method presented herein allows a rapid and very sensitive quantification of resveratrol in mouse plasma at concentrations as low as 500 ppt.

  4. In situ derivatization-ultrasound-assisted dispersive liquid-liquid microextraction for the determination of neurotransmitters in Parkinson's rat brain microdialysates by ultra high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    He, Yongrui; Zhao, Xian-En; Zhu, Shuyun; Wei, Na; Sun, Jing; Zhou, Yubi; Liu, Shu; Liu, Zhiqiang; Chen, Guang; Suo, Yourui; You, Jinmao

    2016-08-05

    Simultaneous monitoring of several neurotransmitters (NTs) linked to Parkinson's disease (PD) has important scientific significance for PD related pathology, pharmacology and drug screening. A new simple, fast and sensitive analytical method, based on in situ derivatization-ultrasound-assisted dispersive liquid-liquid microextraction (in situ DUADLLME) in a single step, has been proposed for the quantitative determination of catecholamines and their biosynthesis precursors and metabolites in rat brain microdialysates. The method involved the rapid injection of the mixture of low toxic bromobenzene (extractant) and acetonitrile (dispersant), which containing commercial Lissamine rhodamine B sulfonyl chloride (LRSC) as derivatization reagent, into the aqueous phase of sample and buffer, and the following in situ DUADLLME procedure. After centrifugation, 50μL of the sedimented phase (bromobenzene) was directly injected for ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) detection in multiple reaction monitoring (MRM) mode. This interesting combination brought the advantages of speediness, simpleness, low matrix effects and high sensitivity in an effective way. Parameters of in situ DUADLLME and UHPLC-MS/MS conditions were all optimized in detail. The optimum conditions of in situ DUADLLME were found to be 30μL of microdialysates, 150μL of acetonitrile containing LRSC, 50μL of bromobenzene and 800μL of NaHCO3-Na2CO3 buffer (pH 10.5) for 3.0min at 37°C. Under the optimized conditions, good linearity was observed with LODs (S/N>3) and LOQs (S/N>10) of LRSC derivatized-NTs in the range of 0.002-0.004 and 0.007-0.015 nmol/L, respectively. It also brought good precision (3.2-12.8%, peak area CVs%), accuracy (94.2-108.6%), recovery (94.5-105.5%) and stability (3.8-8.1%, peak area CVs%) results. Moreover, LRSC derivatization significantly improved chromatographic resolution and MS detection sensitivity of NTs when compared with the

  5. Improved sample treatment for the determination of 17 strong sorbed quinolone antibiotics from compost by ultra high performance liquid chromatography tandem mass spectrometry.

    PubMed

    Dorival-García, N; Labajo-Recio, C; Zafra-Gómez, A; Juárez-Jiménez, B; Vílchez, J L

    2015-06-01

    The use of compost from sewage sludge for agricultural application is nowadays increasing, since composting is recognized as one of the most important recycling options for this material, being a source of nutrients for plants but also of contamination by persistent pollutants. In the present work, a multi-residue analytical method for the determination of 17 quinolone antibiotic residues in compost using multivariate optimization strategies and ultra high performance liquid chromatography-tandem mass spectrometry has been developed. It is based on the use of microwave-assisted extraction at drastic conditions with ACN:m-phosphoric acid (1% w/v) for 5 min at 120°C, in order to achieve a quantitative extraction of the compounds (>76% of extraction recovery). Extracts were cleaned-up by salt-assisted liquid-liquid extraction (SALLE) with NaCl at pH 1.5 (with HClO4) and then using a dispersive sorbent (PSA). After LC separation, the MS conditions, in positive electrospray ionization mode (ESI), were individually optimized for each analyte to obtain maximum sensitivity in the selected reaction monitoring mode (SRM). The analytes were separated in less than 7 min. Cincophen was used as surrogate standard. The limits of detection ranged from 0.2 to 0.5 ng g(-1), and the limits of the quantification from 0.5 to 1.5 ng g(-1), while intra- and inter-day variability (% RSD) was under 7% in all cases. A recovery assay was performed with spiked samples. Recoveries ranging from 95.3% to 106.2% were obtained. Cleanup procedure reduced significantly matrix effects, which constitutes an important achievement, considering the important drawbacks of matrix components in quality and validation parameters. This method was applied to several commercial compost samples. Only 6 of the studied antibiotics were not detected in any of the samples. The antibiotics with the highest concentrations were ciprofloxacin (836 ng g(-1)), ofloxacin (719 ng g(-1)), and enrofloxacin (674 ng g(-1

  6. Validation and Application of an Ultra High-Performance Liquid Chromatography Tandem Mass Spectrometry Method for Yuanhuacine Determination in Rat Plasma after Pulmonary Administration: Pharmacokinetic Evaluation of a New Drug Delivery System.

    PubMed

    Li, Man; Liu, Xiao; Cai, Hao; Shen, Zhichun; Xu, Liu; Li, Weidong; Wu, Li; Duan, Jinao; Chen, Zhipeng

    2016-12-16

    Yuanhuacine was found to have significant inhibitory activity against A-549 human lung cancer cells. However, there would be serious adverse toxicity effects after systemic administration of yuanhuacine, such as by oral and intravenous ways. In order to achieve better curative effect and to alleviate the adverse toxicity effects, we tried to deliver yuanhuacine directly into the lungs. Ultra high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) was used to detect the analyte and IS. After extraction (ether:dichloromethane = 8:1), the analyte and IS were separated on a Waters BEH-C 18 column (100 mm × 2.1 mm, 1.7 μm) under a 5 min gradient elution using a mixture of acetonitrile and 0.1% formic acid aqueous solution as mobile phase at a flow rate of 0.3 mL/min. ESI positive mode was chosen for detection. The method was fully validated for its selectivity, accuracy, precision, stability, matrix effect, and extraction recovery. This new method for yuanhuacine concentration determination in rat plasma was reliable and could be applied for its preclinical and clinical monitoring purpose.

  7. Rapid determination of some psychotropic drugs in complex matrices by tandem dispersive liquid-liquid microextraction followed by high performance liquid chromatography.

    PubMed

    Asghari, Alireza; Fahimi, Ebrahim; Bazregar, Mohammad; Rajabi, Maryam; Boutorabi, Leila

    2017-05-01

    Simple and rapid determinations of some psychotropic drugs in some pharmaceutical wastewater and human plasma samples were successfully accomplished via the tandem dispersive liquid-liquid microextraction combined with high performance liquid chromatography-ultraviolet detection (TDLLME-HPLC-UV). TDLLME of the three psychotropic drugs clozapine, chlorpromazine, and thioridazine was easily performed through two consecutive dispersive liquid-liquid microextractions. By performing this convenient method, proper sample preconcentrations and clean-ups were achieved in just about 7min. In order to achieve the best extraction efficiency, the effective parameters involved were optimized. The optimal experimental conditions consisted of 100μL of CCl 4 (as the extraction organic solvent), and the pH values of 13 and 2 for the donor and acceptor phases, respectively. Under these optimum experimental conditions, the proposed TDLLME-HPLC-UV technique provided a good linearity in the range of 5-3000ngmL -1 for the three psychotropic drugs with the correlation of determinations (R 2 s) higher than 0.996. The limits of quantification (LOQs) and limits of detection (LODs) obtained were 5.0ngmL -1 and 1.0-1.5ngmL -1 , respectively. Also the proper enrichment factors (EFs) of 96, 99, and 88 for clozapine, chlorpromazine, and thioridazine, respectively, and good extraction repeatabilities (relative standard deviations below 9.3%, n=5) were obtained. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Quantitative determination of tilmicosin in canine serum by high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Herrera, Michael; Ding, Haiqing; McClanahan, Robert; Owens, Jane G; Hunter, Robert P

    2007-09-15

    A highly sensitive and quantitative LC/MS/MS assay for the determination of tilmicosin in serum has been developed and validated. For sample preparation, 0.2 mL of canine serum was extracted with 3 mL of methyl tert-butyl ether. The organic layer was transferred to a new vessel and dried under nitrogen. The sample was then reconstituted for analysis by high performance liquid chromatography-tandem mass spectrometry. A Phenomenex Luna C8(2) analytical column was used for the chromatographic separation. The eluent was subsequently introduced to the mass spectrometer by electrospray ionization. A single range was validated for 50-5000 ng/mL for support of toxicokinetic studies. The inter-day relative error (inaccuracy) for the LLOQ samples ranged from -5.5% to 0.3%. The inter-day relative standard deviations (imprecision) at the respective LLOQ levels were < or =10.1%.

  9. [Simultaneous determination of sixteen perfluorinated organic compounds in surface water by solid phase extraction and ultra performance liquid chromatography with electrospray ionization tandem mass spectrometry].

    PubMed

    Zhang, Ming; Tang, Fangliang; Yu, Yayun; Chen, Feng; Xu, Jianfen; Ye, Yonggen

    2014-05-01

    A high-throughput detection method has been developed for the determination of sixteen perfluorinated organic compounds (PFCs) in surface water by solid phase extraction-ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (SPE-UPLC-ESI-MS/MS). The water samples were concentrated and purified through WAX solid phase extraction cartridges. The UPLC separation was performed on an ACQUITY UPLC BEH C18 column utilizing a gradient elution program of methanol (containing 2 mmol/L ammonium acetate) and water (containing 2 mmol/L ammonium acetate) as the mobile phases at a flow rate of 0.4 mL/min. The MS/MS detection was performed under negative electrospray ionization ( ESI ) in multiple reaction monitoring (MRM) mode. Good linearities were observed in the range of 0.5-100 gg/L or 1.0 - 100 microg/L with correlation coefficients from 0.998 7 to 0.999 9. The limits of detection (LODs) for the sixteen perfluorinated organic compounds were in the range of 0.06-0.46 ng/L. The recoveries ranged from 67.6% to 103% with the relative standard deviations between 2.94% and 12.0%. This method was characterized by high sensitivity and precision, extensive range and high speed, and can be applied for the analysis of PFC contaminants in surface water.

  10. A novel ultra high-performance liquid chromatography-tandem mass spectrometry method for the simultaneous determination of xanthones and steroidal saponins in crude and salt-processed Anemarrhenae Rhizoma aqueous extracts.

    PubMed

    Ji, De; Su, Xiaonan; Huang, Ziyan; Wang, Qiaohan; Lu, Tulin

    2018-06-01

    We established a rapid and sensitive ultra high-performance liquid chromatography tandem mass spectrometry method for the simultaneous quantification of xanthones and steroidal saponins in rat plasma. Chromatographic separation was achieved on a C 18 column with a mobile phase comprising acetonitrile and 0.1% formic acid. The detection was performed by negative electrospray ionization in multiple reaction monitoring mode. The validated method showed good linearity within the tested range (r > 0.9945). The intra- and interday precision at high, medium, and low concentrations was less than 7.96%. The bias of accuracies ranged from -1.92 to 9.62%. The extraction recoveries of the compounds ranged from 84.78 to 88.69%, and the matrix effects ranged from 96.76 to 108.59%. This method was successfully applied to a pharmacokinetic comparison of crude and salt-processed Anemarrhenae Rhizoma aqueous extracts after oral administration in rats. The maximum plasma concentration and area under concentration-time curve of timosaponin BIII and timosaponin AIII increased significantly (P < 0.05 or 0.01) and those of timosaponin BII decreased significantly (P < 0.05) after processing. These results could contribute to the clinical application of crude and salt-processed Anemarrhenae Rhizoma and reveal the processing mechanism. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. [Determination of 250 pesticide residues in vegetables using QuEChERS-ultra performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Zhang, Aizhi; Wang, Quanlin; Cao, Lili; Li, Yu; Shen, Hao; Shen, Jian; Zhang, Shufen; Man, Zhengyin

    2016-02-01

    A multiresidue analytical method for the determination of 250 pesticide residues in vegetables was developed by using QuEChERS-ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The target compounds were extracted with acetonitrile containing 1% (v/v) acetic acid, purified by a mixed sorbent of MgSO4, primary secondary amine (PSA), graphitized carbon black (GCB) and C18, separated on a Waters ACQUITY™ UPLC BEH C18 column (100 mm x 2. 1 mm, 1.7 µm) and detected by UPLC-MS/MS. Anhydrous magnesium sulfate was used as a dewatering agent. The effects of the amounts of MgSO4, PSA, GCB and C18 added on the recoveries of 250 pesticides were investigated. The results showed that the purification effect was best when 300 mg MgSO4, 200 mg PSA, 10 mg GCB and 100 mg C18 in 2 mL of the extract were added. For the 250 pesticide residues, the limits of detection (LODs) of the method were from 0. 01 to 50. 00 g/kg. The recoveries obtained ranged from 60. 1% to 120% at three spiked levels in Chinese chives with the relative standard deviations between 3. 5% and 19. 5% using matrix matched external standard method. The results showed that the method is able to meet requirements of the multiresidue detection of the 250 pesticides in vegetable. The method has the advantages of rapidity, simplicity, high sensitivity and better purification effect. It is suitable for the rapid determination of the common pesticides in vegetables, and it provides a strong guarantee for the risk assessments of the quality and safety of vegetables.

  12. Analysis of legal high materials by ultra-performance liquid chromatography with time of flight mass spectrometry as part of a toxicology vigilance system: what are the most popular novel psychoactive substances in the UK?

    PubMed

    Ford, Loretta T; Berg, Jonathan D

    2017-03-01

    Introduction Legal highs also known as novel psychoactive substances mimic the effects of classic drugs of abuse. Challenges to developing screening services for novel psychoactive substances include identifying which novel psychoactive substances are available to target. Using new techniques such as exact mass time of flight can help identify common novel psychoactive substances to target for screening patient samples by routine methods such as tandem mass spectrometry. We demonstrate this strategy working in our own clinical toxicology laboratory after qualitative analysis of 98 suspect materials for novel psychoactive substances by ultra-performance liquid chromatography with time of flight mass spectrometry. Results From July 2014 to July 2015 we received 98 requests to test a range of different suspect materials for novel psychoactive substances including herbs, tobacco, liquids, pills and powders. Overall, 87% of the suspect materials tested positive for novel psychoactive substances, and 15% for controlled drugs. Three common novel psychoactive substances were present in 74% of the suspect materials: methiopropamine, a methamphetamine analogue; ethylphenidate, a cocaine mimic; and the third generation synthetic cannabinoid 5F-AKB-48. For the 55 branded products we tested only 24% of the stated contents matched exactly the compounds we detected. Conclusion Testing suspect materials using ultra-performance liquid chromatography with time of flight mass spectrometry has identified three common novel psychoactive substances in use in the UK, simplifying the development of a relevant novel psychoactive substances screening service to our population. By incorporating this into our routine liquid chromatography tandem mass spectrometry drugs of abuse screen, then offers a clinically relevant novel psychoactive substances service to our users. This strategy ensures our clinical toxicology service continues to remain effective to meet the challenges of the changing

  13. [Determination of antibiotics in oral hygiene products by high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Zhou, Weijun; Xie, Zhengfu; Shao, Linzhi

    2012-07-01

    A high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/ MS) method was developed for simultaneous determination of 13 antibiotics in oral hygiene products, including five tetracyclines, three macrolides, two quinolones, one beta-lactam and two lincosamides. The sample was extracted with 0.1% (volume percentage, same hereinafter) formic acid-acetonitrile (95:5, v/v), then centrifuged, filtered and diluted. The target compounds were separated on a C18 column (150 mm x 2.1 mm, 5 microm) with a gradient elution of 0. 1% formic acid and acetonitrile as the mobile phases, and detected by tandem mass spectrometry in positive electrospray ionization and multiple reaction monitoring (MRM) mode. The quantification of 13 antibiotics was performed by the external standard method. The calibration curves showed good linearity in the range of 5.0-50.0 microg/L with detection limits of 10.0 mg/kg. The recoveries of antibiotics in mouthwash and toothpaste samples at the three spiked levels of 10, 20 and 100 mg/kg were in the range of 80.1%-115% with the relative standard deviations in the range of 0.94%-8.69%. This method is accurate, reliable, simple, and suitable for the analysis of antibiotics in oral hygiene products.

  14. Simple and sensitive determination of hydrazine in drinking water by ultra-high-performance liquid chromatography-tandem mass spectrometry after derivatization with naphthalene-2,3-dialdehyde.

    PubMed

    Oh, Jin-Aa; Shin, Ho-Sang

    2015-05-22

    An ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was developed to determine the level of hydrazine in drinking water. The method is based on the derivatization of hydrazine with naphthalene-2,3-dicarboxaldehyde (NDA) in water. The optimum conditions for UPLC-MS/MS detection were determined as follows: derivatization reagent dosage, 50mg/L of NDA; pH 2; and reaction time, 1min; room temperature. The formed derivative was injected into an LC system without extraction or purification procedures. Under the established conditions, the method was used to detect hydrazine in raw drinking water and chlorinated drinking water. The limits of detection and quantification for hydrazine in drinking water were 0.003μg/L and 0.01μg/L, respectively. The accuracy was in the range of 97-104%, and precision, expressed as relative standard deviation, was less than 9% in drinking water. Hydrazine was detected at a concentration of 0.13μg/L in one sample among 24 raw drinking water samples and in a range of 0.04-0.45μg/L in three samples among 24 chlorinated drinking water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Analysis of methyloxime derivatives of intact esters of testosterone and boldenone in equine plasma using ultra high performance liquid chromatography tandem mass spectrometry.

    PubMed

    Gray, Bobby P; Teale, Phil; Pearce, Clive M

    2011-04-01

    Analysis of equine plasma samples to detect the abuse of anabolic steroids can be complicated when the parent steroid is endogenous to the animal. Anabolic steroids are usually administered intramuscularly as synthetic esters and therefore detection of the exogenous esters provides unequivocal proof of illegal administration. An ultra high performance liquid chromatography tandem mass spectrometric (UPLC-MSMS) method for the analysis of esters of testosterone (propionate, phenylpropionate, isocaproate, and decanoate) and boldenone (undecylenate) in equine plasma has been developed. Esters were extracted from equine plasma using a mixture of hexane and ethyl acetate and treated with methoxyamine hydrochloride to form methyloxime derivatives. Metenolone enanthate was used as an internal standard. After chromatographic separation, the derivatized steroid esters were quantified using selected reaction monitoring (SRM). The limit of detection for all of the steroid esters, based on a signal to noise ratio (S/N) of 3:1, was 1-3 pg/mL. The lower limit of quantification (LLOQ) for the all of the steroid esters was 5 pg/mL when 2 mL of plasma was extracted. Recovery of the steroid esters was 85-97% for all esters except for testosterone decanoate which was recovered at 62%. The intra-day coefficient of variation (CV) for the analysis of plasma quality control (QC) samples was less than 9.2% at 40 pg/mL and less than 6.0% at 400 pg/mL. The developed assay was used to successfully confirm the presence of intact testosterone esters in equine plasma samples following intramuscular injection of Durateston® (mixed testosterone esters). Copyright © 2011 John Wiley & Sons, Ltd.

  16. Simultaneous determination of blonanserin and its four metabolites in human plasma using ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhou, Ying; Liu, Ming; Jiang, Ji; Wang, Hongyun; Hu, Pei

    2013-11-15

    A sensitive and rapid method based on ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) was developed and validated for the simultaneous determination of blonanserin, its major active metabolite (N-deethyl form) and other three metabolites (N-oxide form, Ethylenediamine form and Carboxylate form) in human plasma. Plasma samples were pre-purified by solid-phase extraction (SPE) and analyzed using a gradient chromatographic separation over an Acquity UPLC CSH C18 column. The mobile phase consisted of acetonitrile-water containing 5mM ammonium formate and 0.1% formic acid at a flow rate of 0.5mL/min. Positive electrospray ionization was employed as the ionization source in the multiple reaction monitoring (MRM) mode. The analysis time was about 3.5min. The method was fully validated over the concentration range of 0.01-1ng/mL for all analytes. The lower limit of quantification (LLOQ) was 0.01ng/mL. Inter- and intra-batch precision was less than 15% and the accuracy was within 85-115%. The mean extraction recoveries of all analytes at two concentration levels were consistent. Selectivity, matrix effect and stability were also validated. The method was applied to the pharmacokinetic study of blonanserin in Chinese healthy subjects. Copyright © 2013 Elsevier B.V. All rights reserved.

  17. [Determination of strobilurin fungicides in fruits and their mass fragmentation routes by ultra performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Zhou, Yao; Yang, Huiqin; Shi, Yiyin; Chen, Jiaxian; Zhu, Jian; Deng, Xiaojun; Guo, Dehua

    2017-09-08

    A method was developed for the simultaneous determination of six strobilurin fungicide ( E -metominostrobin, azoxystrobin, kresoxim-methyl, picoxystrobin, pyraclostrobin and trifloxystrobin) residues in orange, banana, apple and pineapple samples by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The fragmentation routes of all the compounds were explained by the aid of a fragment predicting software ACD Lab/MS Fragmenter. The samples were extracted by acetonitrile, then cleaned up by amino solid phase extraction cartridges (SupelClean LC-NH 2 ). The extracts were separated on a ACQUITY UPLC BEH C 18 column (50 mm×2.1 mm, 1.7 μm) with gradient elution. Acetonitrile containing 0.1% (v/v) formic acid and 10 mmol/L ammonium acetate containing 0.1% (v/v) formic acid were used as mobile phases. The samples were detected by electrospray ionization (ESI)-MS/MS in positive ion and multiple reaction monitoring (MRM) mode, quantified by external standard method. Good linearities were obtained in the range of 5-100 μg/L (for pyraclostrobin, 1-20 μg/L) with correlation coefficients ( r 2 ) greater than 0.999. The recoveries ranged from 60.4% to 120% with the relative standard deviations between 2.15% and 15.1% ( n =6). The developed method can meet the inspection of the six strobilurin residues in the orange, banana, apple and pineapple samples.

  18. Ultra-performance liquid chromatography-tandem mass spectrometry-based multiplex enzyme assay for six enzymes associated with hereditary hemolytic anemia.

    PubMed

    Park, Chul Min; Lee, Kyunghoon; Jun, Sun-Hee; Song, Sang Hoon; Song, Junghan

    2017-08-15

    Deficiencies in erythrocyte metabolic enzymes are associated with hereditary hemolytic anemia. Here, we report the development of a novel multiplex enzyme assay for six major enzymes, namely glucose-6-phosphate dehydrogenase, pyruvate kinase, pyrimidine 5'-nucleotidase, hexokinase, triosephosphate isomerase, and adenosine deaminase, deficiencies in which are implicated in erythrocyte enzymopathies. To overcome the drawbacks of traditional spectrophotometric enzyme assays, the present assay was based on ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The products of the six enzymes were directly measured by using ion pairing UPLC-MS/MS, and the precision, linearity, ion suppression, optimal sample amounts, and incubation times were evaluated. Eighty-three normal individuals and 13 patients with suspected enzymopathy were analyzed. The UPLC running time was within 5min. No ion suppression was observed at the retention time for the products or internal standards. We selected an optimal dilution factor and incubation time for each enzyme system. The intra- and inter-assay imprecision values (CVs) were 2.5-12.1% and 2.9-14.3%, respectively. The linearity of each system was good, with R 2 values >0.97. Patient samples showed consistently lower enzyme activities than those from normal individuals. The present ion paring UPLC-MS/MS assay enables facile and reproducible multiplex evaluation of the activity of enzymes implicated in enzymopathy-associated hemolytic anemia. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Simultaneous determination of AM80 (tamibarotene) and WJD-A-1 in rat plasma by ultra high-performance liquid chromatography-tandem mass spectrometry and its application to a pharmacokinetic study.

    PubMed

    Leng, Ping; Yang, Zhao; Ma, Baohua; Li, Jing; Sun, Jialin; Xie, Yiming; Sun, Yong

    2018-03-05

    A compound (WJD-A-1) was previously reported as a candidate prodrug of Am80 (tamibarotene), which was approved in Japan in 2005 as a therapeutic agent for recurrent refractory acute promyelocytic leukaemia. A rapid, selective and sensitive ultra high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed for the first time to simultaneously determine WJD-A-1 and its major phase-I metabolites AM80 in rat plasma. After a simple sample preparation procedure by protein precipitation with methanol and acetonitrile, WJD-A-1, AM80 and the internal standard were chromatographed on an ACQUITY UPLC TM BEH C 18 column. The mobile phase consisted of methanol-0.1% formic acid (80:20, v/v) and the flow rate was 0.20 mL/min. The detection was performed on a triple quadrupole tandem mass spectrometer by multiple reaction monitoring (MRM) mode via electrospray ionization (ESI) source. Each plasma sample was chromatographed within 2.6 min. The linear calibration curves for WJD-A-1 and the AM80 were obtained in the concentration range of 5.40-5.40 × 10 3 and 5.08-5.08 × 10 3  ng/mL, respectively (r ≥ 0.99). The intra- and inter-day precision (relative standard deviation, RSD) values were less than 8% and the accuracy (relative error, RE) was within ±6.8%, determined from quality control (QC) samples for the analytes. The method herein described was fully validated and successfully applied to pharmacokinetic study of WJD-A-1 following an intravenous administration of 300 μg/kg WJD-A-1 to rats.

  20. Study on pharmacokinetics of 3,4-divanillyltetrahydrofuran in rats by ultra-fast liquid chromatography/tandem mass spectrometry.

    PubMed

    Shan, Chen-Xiao; Cui, Xiao-Bing; Yu, Sheng; Chai, Chuan; Wen, Hong-Mei; Wang, Xin-Zhi; Sun, Xue

    2016-01-01

    3,4-Divanillyltetrahydrofuran is the main active ingredient of nettle root which can increase steroid hormones in the bloodstream for many of bodybuilders. To better understand its pharmacological activities, we need to determine its pharmacokinetic profiles. In this study, a rapid and sensitive ultra-fast liquid chromatography-tandem mass spectrometry (UFLC-MS/MS) method has been developed for the determination of 3,4-divanillyltetrahydrofuran in the plasma of rats. Chromatographic separation was performed on a C18 column at 40°C, with a gradient elution consisting of methanol and water containing 0.3% (v/v) formic acid at a flow rate of 0.8mL/min. The detection was performed using an electrospray triple-quadrupole MS/MS via positive ion multiple reaction monitoring mode. The lower limits-of-quantification determined were 0.5ng/mL. The intra- and inter-day precision (RSD%) was found to be within 15% and the accuracy (RE%) ranged from -4.0% to 7.0%. This simple yet sensitive method was fully validated and could be successfully applied to the study on pharmacokinetics of 3, 4-divanillyltetrahydrofuran. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Determination of perfluorocompounds in popcorn packaging by pressurised liquid extraction and ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Martínez-Moral, María Pilar; Tena, María Teresa

    2012-11-15

    The development and characterisation of a method based on reverse-phase ultra-performance liquid chromatography (UPLC) coupled to a quadrupole-time of flight mass spectrometer (Q-TOF-MS) with negative electrospray ionisation (ESI) to determine perfluorinated compounds (PFCs) in packaging is presented in this paper. Analytes were quantitatively recovered from packaging with methanol in only one PLE cycle of 6 min at 100 °C. The UPLC allowed the successful separation of the studied PFCs in less than 4 min. The whole method presented good precision, with RSDs below 8%, LODs from 0.6 to 16 ng g(-1); and excellent recovery values, around 100% in all cases, were achieved. The PLE-UPLC-MS method was applied to the analysis of popcorn packaging for microwave cooking. Besides the most commonly studied PFCs: PFOA and PFOS, the presence of other perfluorocarboxylic acids (PFCAs) in popcorn packaging is evidenced in this work. Copyright © 2012 Elsevier B.V. All rights reserved.

  2. Comprehensive comparison of liquid chromatography selectivity as provided by two types of liquid chromatography detectors (high resolution mass spectrometry and tandem mass spectrometry): "where is the crossover point?".

    PubMed

    Kaufmann, A; Butcher, P; Maden, K; Walker, S; Widmer, M

    2010-07-12

    The selectivity of mass traces obtained by monitoring liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was compared. A number of blank extracts (fish, pork kidney, pork liver and honey) were separated by ultra performance liquid chromatography (UPLC). Detected were some 100 dummy transitions respectively dummy exact masses (traces). These dummy masses were the product of a random generator. The range of the permitted masses corresponded to those which are typical for analytes (e.g. veterinary drugs). The large number of monitored dummy traces ensured that endogenous compounds present in the matrix extract, produced a significant number of detectable chromatographic peaks. All obtained chromatographic peaks were integrated and standardized. Standardisation was done by dividing these absolute peak areas by the average response of a set of 7 different veterinary drugs. This permitted a direct comparison between the LC-HRMS and LC-MS/MS data. The data indicated that the selectivity of LC-HRMS exceeds LC-MS/MS, if high resolution mass spectrometry (HRMS) data is recorded with a resolution of 50,000 full width at half maximum (FWHM) and a corresponding mass window. This conclusion was further supported by experimental data (MS/MS based trace analysis), where a false positive finding was observed. An endogenous matrix compound present in honey matrix behaved like a banned nitroimidazole drug. This included identical retention time and two MRM traces, producing an MRM ratio between them, which perfectly matched the ratio observed in the external standard. HRMS measurement clearly resolved the interfering matrix compound and unmasked the false positive MS/MS finding. Copyright 2010 Elsevier B.V. All rights reserved.

  3. The application of chiral ultra-high-performance liquid chromatography tandem mass spectrometry to the separation of the zoxamide enantiomers and the study of enantioselective degradation process in agricultural plants.

    PubMed

    Pan, Xinglu; Dong, Fengshou; Chen, Zenglong; Xu, Jun; Liu, Xingang; Wu, Xiaohu; Zheng, Yongquan

    2017-11-24

    In this study, an effective and sensitive chiral analytical method was developed to detect zoxamide enantiomers in vegetables, fruits and environmental matrices using ultra-high-performance liquid chromatography-tandem mass spectrometry. Optimal separation conditions were achieved with Lux Amylose-2 chiral column using acetonitrile/water (70:30v/v) as mobile phase with a flow rate and column temperature of 0.5mL/min and 25°C. The absolute configuration, optical rotation and elution order were confirmed for the first time. The average recoveries in all matrices at four spiking levels (0.5, 5, 50, 250μg/kg) ranged from 89.7 to 117.4%, with relative standard deviations being less than 10.9% for two enantiomers. The enantioselective dissipation of zoxamide in tomato showed that (-)-R-zoxamide was preferentially degraded leading to an enrichment of (+)-S-isomer, with half-lives of 3.80 d and 5.17 d, respectively. Inversely, (+)-S-zoxamide degraded faster than (-)-R-zoxamide in pepper (1.95day and 2.28day, respectively) and grape (2.03day and 2.87day). No significant enantioselectivity was observed in cucumber. The results of this study could help facilitate more accurate risk assessments of zoxamide in the future. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Determination of oxycodone and its major metabolites noroxycodone and oxymorphone by ultra-high-performance liquid chromatography tandem mass spectrometry in plasma and urine: application to real cases.

    PubMed

    Pantano, Flaminia; Brauneis, Stefano; Forneris, Alexandre; Pacifici, Roberta; Marinelli, Enrico; Kyriakou, Chrystalla; Pichini, Simona; Busardò, Francesco Paolo

    2017-08-28

    Oxycodone is a narcotic drug widely used to alleviate moderate and severe acute and chronic pain. Variability in analgesic efficacy could be explained by inter-subject variations in plasma concentrations of parent drug and its active metabolite, oxymorphone. To evaluate patient compliance and to set up therapeutic drug monitoring (TDM), an ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) assay was developed and validated for the parent drug and its major metabolites noroxycodone and oxymorphone. Extraction of analytes from plasma and urine samples was obtained by simple liquid-liquid extraction. The chromatographic separation was achieved with a reversed phase column using a linear gradient elution with two solvents: acetic acid 1% in water and methanol. The separated analytes were detected with a triple quadrupole mass spectrometer operated in multiple reaction monitoring (MRM) mode via positive electrospray ionization (ESI). Separation of analytes was obtained in less than 5 min. Linear calibration curves for all the analytes under investigation in urine and plasma samples showed determination coefficients (r2) equal or higher than 0.990. Mean absolute analytical recoveries were always above 86%. Intra- and inter-assay precision (measured as coefficient of variation, CV%) and accuracy (measured as % error) values were always better than 13%. Limit of detection at 0.06 and 0.15 ng/mL and limit of quantification at 0.2 and 0.5 ng/mL for plasma and urine samples, respectively, were adequate for the purpose of the present study. Rapid extraction, identification and quantification of oxycodone and its metabolites both in urine and plasma by UHPLC-MS/MS assay was tested for its feasibility in clinical samples and provided excellent results for rapid and effective drug testing in patients under oxycodone treatment.

  5. Profiling ABA metabolites in Nicotiana tabacum L. leaves by ultra-performance liquid chromatography-electrospray tandem mass spectrometry.

    PubMed

    Turecková, Veronika; Novák, Ondrej; Strnad, Miroslav

    2009-11-15

    We have developed a simple method for extracting and purifying (+)-abscisic acid (ABA) and eight ABA metabolites--phaseic acid (PA), dihydrophaseic acid (DPA), neophaseic acid (neoPA), ABA-glucose ester (ABAGE), 7'-hydroxy-ABA (7'-OH-ABA), 9'-hydroxy-ABA (9'-OH-ABA), ABAaldehyde, and ABAalcohol--before analysis by a novel technique for these substances, ultra-performance liquid chromatography-electrospray ionisation tandem mass spectrometry (UPLC-ESI-MS/MS). The procedure includes addition of deuterium-labelled standards, extraction with methanol-water-acetic acid (10:89:1, v/v), simple purification by Oasis((R)) HLB cartridges, rapid chromatographic separation by UPLC, and sensitive, accurate quantification by MS/MS in multiple reaction monitoring modes. The detection limits of the technique ranged between 0.1 and 1 pmol for ABAGE and ABA acids in negative ion mode, and 0.01-0.50 pmol for ABAGE, ABAaldehyde, ABAalcohol and the methylated acids in positive ion mode. The fast liquid chromatographic separation and analysis of ABA and its eight measured derivatives by UPLC-ESI-MS/MS provide rapid, accurate and robust quantification of most of the substances, and the low detection limits allow small amounts of tissue (1-5mg) to be used in quantitative analysis. To demonstrate the potential of the technique, we isolated ABA and its metabolites from control and water-stressed tobacco leaf tissues then analysed them by UPLC-ESI-MS/MS. Only ABA, PA, DPA, neoPA, and ABAGE were detected in the samples. PA was the most abundant analyte (ca. 1000 pmol/g f.w.) in both the control and water-stressed tissues, followed by ABAGE and DPA, which were both present at levels ca. 5-fold lower. ABA levels were at least 100-fold lower than PA concentrations, but they increased following the water stress treatment, while ABAGE, PA, and DPA levels decreased. Overall, the technique offers substantial improvements over previously described methods, enabling the detailed, direct study of

  6. Ultra high performance liquid chromatography tandem mass spectrometry determination and profiling of prohibited steroids in human biological matrices. A review.

    PubMed

    Gosetti, Fabio; Mazzucco, Eleonora; Gennaro, Maria Carla; Marengo, Emilio

    2013-05-15

    list of the prohibited substances of the World Anti-Doping Agency (WADA). In WADA list steroids figure in three main classes, namely anabolic steroids, corticosteroids and substances with anti-estrogenic properties. It must be strongly reminded that assumption of doping agents not only leads to athletes the possible failing of doping tests but causes important health risk and WADA prohibited list establishes criteria to highlight the alteration of the natural steroid profile caused by exogenous administration. Doping control analyses are generally performed in urine, a matrix that provides a prolonged detection time window, and less often in blood, serum, plasma, hair, saliva, and nails. To identify the chemical structures of anabolic steroids the use of mass spectrometry detection is very advantageous. Gas chromatography-mass spectrometry (GC-MS) techniques allowed for the development of comprehensive screening methods. GC-MS methods are sensitive and robust but present the disadvantages of time-consuming sample pretreatment, that is often based on hydrolysis and derivatisation reactions. Liquid chromatography-mass spectrometry (LC-MS) methods have been successfully used to identify and determinate steroids in different matrices, as well as to study their metabolisms. Nowadays, automatic rapid ultra high performance liquid chromatography (UHPLC) tandem mass spectrometry has become the technique of choice for steroid analysis. Due to its generally higher speed, sensitivity, reproducibility and specificity with respect to HPLC, it can be used to simultaneously separate and determinate multi component steroid mixtures. The technique is of huge interest to separate conjugates anabolic androgenic steroids, as it allows efficiency enhancement due to the small particle (sub-2μm) column packing, which provides high peak capacity within analysis times even 5-10 fold shorter than conventional HPLC methods. Modern multiplex instruments can analyze thousands of samples per month

  7. Simultaneous Quantification of 11 Constituents in Wuji Pill Using Ultra Performance Liquid Chromatography Coupled With a Triple Quadrupole Electrospray Tandem Mass Spectrometry.

    PubMed

    Tian, Tingting; Jin, Yiran; Ma, Yinghua; Xie, Weiwei; Xu, Huijun; Du, Yingfeng

    2016-02-01

    An ultra performance liquid chromatography coupled with a triple quadrupole electrospray tandem mass spectrometry (UPLC-MS-MS) method was developed for analyzing and identifying the constituents of 11 compounds including berberine, epiberberine, berberrubine, jatrorrhizine, coptisine, palmatine, evodiamine, rutaecarpine, limonin, paeoniflorin and albiflorin in Wuji pill (WJ pill), a traditional Chinese medicine. The chromatographic separation was performed on a C18 column and the mobile phase was composed of water (0.1% formic acid and 2 mmol ammonium acetate) and methanol with a linear gradient elution. The detection was performed by multiple reaction monitoring mode, using electrospray ionization in the positive ion mode. The total run time was 14 min. The calibration curves were linear with all correlation coefficients higher than 0.9987 in the tested range. The intra- and interday precisions were no more than 4.9%, and the average recoveries were from 92.4 to 107.8% with the relative standard deviations no more than 7.8%. The developed method was successfully employed to analyze five batches of WJ pill samples. This is the first time to establish a method for the quality control of WJ pill to ensure the safety and efficacy in clinical applications effectively. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  8. [Simultaneous determination of six synthetic sweeteners in food by high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Liu, Xiaoxi; Ding, Li; Liu, Jinxia; Zhang, Ying; Huang, Zhiqiang; Wang, Libing; Chen, Bo

    2010-11-01

    A simple and sensitive method for the determination of six synthetic sweeteners (sodium cyclamate, saccharin sodium, acesulfame-K, aspartame, alitame and neotame) in food was developed. The synthetic sweeteners were extracted by methanol-water (1 : 1, v/v). The extract was separated on a C18 column using 0.1% (v/v) formic acid-5 mmol/L ammonium formate/acetonitrile as mobile phase, and then detected by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) using multiple reaction monitoring (MRM) mode. The good linearities (r > 0.998) were achieved for all the analytes over the range of 20-500 microg/L. The recoveries obtained ranged from 81.3% to 106.0% at three spiked concentrations, with the relative standard deviations lower than 11%. The established method has been successfully applied to the determination of synthetic sweeteners in food.

  9. Quantitative analysis of the major constituents in Chinese medicinal preparation SuoQuan formulae by ultra fast high performance liquid chromatography/quadrupole tandem mass spectrometry

    PubMed Central

    2013-01-01

    Background The SuoQuan formulae containing Fructus Alpiniae Oxyphyllae has been used to combat the urinary incontinence symptoms including frequency, urgency and nocturia for hundreds of years in China. However, the chemical information was not well characterized. The quality control marker constituent only focused on one single compound in the current Chinese Pharmacopeia. Hence it is prudent to identify and quantify the main constituents in this herbal product. This study aimed to analyze the main constituents using ultra-fast performance liquid chromatography coupled to tandem mass spectrometry (UFLC-MS/MS). Results Fourteen phytochemicals originated from five chemical classes constituents were identified by comparing the molecular mass, fragmentation pattern and retention time with those of the reference standards. A newly developed UFLC-MS/MS was validated demonstrating that the new assay was valid, reproducible and reliable. This method was successfully applied to simultaneously quantify the fourteen phytochemicals. Notably, the content of these constituents showed significant differences in three pharmaceutical preparations. The major constituent originated from each of chemical class was isolinderalactone, norisoboldine, nootkatone, yakuchinone A and apigenin-4’,7-dimethylther, respectively. The variation among these compounds was more than 1000 times. Furthermore, the significant content variation between the two different Suoquan pills was also observed. Conclusion The proposed method is sensitive and reliable; hence it can be used to analyze a variety of SuoQuan formulae products produced by different pharmaceutical manufacturers. PMID:23899222

  10. Simple and rapid determination of norethindrone in human plasma by supported liquid extraction and ultra performance liquid chromatography with tandem mass spectrometry.

    PubMed

    Gong, Zhilong; Chandler, Kiresha; Webster, Stephen; Kerley, Remy; Buist, Susan; McCort-Tipton, Melanie

    2012-03-15

    We report for the first time an ultra performance liquid chromatographic method with tandem mass spectrometric detection (UPLC/MS/MS) for the determination of norethindrone alone in human plasma over the concentration range of 50.0-25000 pg mL(-1) using a sample volume of 0.250 mL. Norethindrone and its internal standard (ISTD), norethindrone-(13)C(2), were extracted from human plasma by supported liquid extraction (SLE). After evaporation of the organic solvent, samples were reconstituted and analyzed on an UPLC/MS/MS system. The UPLC system used a Waters BEH C18 (100 mm × 2.1mm, 1.7 μm) column with mobile phase A of 0.05% formic acid in water:acetonitrile (65:35, v/v) and mobile phase B of 0.05% formic acid in methanol:acetonitrile (50:50, v/v). The flow rate was 0.500 mL min(-1). The method was fully validated. The inter-run accuracy and precision at the lower limit of quantitation (LLOQ), low, mid and high quality control (QC) concentration levels were 99.2-108.4% with a <8.1% CV (coefficient of variation), respectively. The validated method has been successfully applied to analysis of thousands of pharmacokinetic samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  11. Development and validation of a measurement procedure based on ultra-high performance liquid chromatography-tandem mass spectrometry for simultaneous measurement of β-lactam antibiotic concentration in human plasma.

    PubMed

    Rigo-Bonnin, Raül; Ribera, Alba; Arbiol-Roca, Ariadna; Cobo-Sacristán, Sara; Padullés, Ariadna; Murillo, Òscar; Shaw, Evelyn; Granada, Rosa; Pérez-Fernández, Xosé L; Tubau, Fe; Alía, Pedro

    2017-05-01

    The administration of β-lactam antibiotics in continuous infusion could let optimize the pharmacokinetic/pharmacodynamic parameters, especially in the treatment of serious bacterial infections. In this context, and also due to variability in their plasmatic concentrations, therapeutic drug monitoring (TDM) may be useful to optimize dosing and, therefore, be useful for the clinicians. We developed and validated a measurement procedure based on ultra-high performance liquid chromatography-tandem mass spectrometry for simultaneous measurement of amoxicillin, ampicillin, cloxacillin, piperacillin, cefepime, ceftazidime, cefuroxime, aztreonam and meropenem concentrations in plasma. The chromatographic separation was achieved using an Acquity®-UPLC® BEH™ (2.1×100mm id, 1.7μm) reverse-phase C 18 column, with a water/acetonitrile linear gradient containing 0.1% formic acid at a 0.4mL/min flow rate. β-Lactam antibiotics and their internal standards were detected by electrospray ionization mass spectrometry in multiple reaction monitoring mode. Chromatography run time was 7.0min and β-lactam antibiotics eluted at retention times ranging between 1.08 and 1.91min. The lower limits of quantification were between 0.50 and 1.00mg/L. Coefficients of variation and relative bias absolute values were <13.3% and 14.7%, respectively. Recovery values ranged from 55.7% to 84.8%. Evaluation of the matrix effect showed ion enhancement for all antibiotics. No interferences or carry-over were observed. Our measurement procedure could be applied to daily clinical laboratory practice to measure the concentration of β-lactam antibiotics in plasma, for instance in patients with bone and joint infections and critically ill patients. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Quantification and semiquantification of multiple representative components for the holistic quality control of Allii Macrostemonis Bulbus by ultra high performance liquid chromatography with quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    Qin, Zifei; Lin, Pei; Dai, Yi; Yao, Zhihong; Wang, Li; Yao, Xinsheng; Liu, Liyin; Chen, Haifeng

    2016-05-01

    Allii Macrostemonis Bulbus (named Xiebai in China) is a folk medicine with medicinal values for the treatment of thoracic obstruction and cardialgia, and a food additive as well. However, there is even no quantitative standard for Allii Macrostemonis Bulbus recorded in the current edition of the Chinese Pharmacopeia. Hence, simultaneous assay of multiple components is urgent. In this study, chemometric methods were firstly applied to discover the components with significant fluctuation among multiple Allii Macrostemonis Bulbus samples based on optimized fingerprints. Meanwhile, the major components and main absorbed components in rats were all selected as its representative components. Subsequently, a sensitive method was established for the simultaneous determination of 54 components (15 components for quantification and 39 components for semiquantification) by ultra high performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry. Moreover, the validated method was successfully applied to evaluate the quality of multiple samples on the market. It became known that multiple Allii Macrostemonis Bulbus samples varied significantly and showed poor consistency. This work illustrated that the proposed approach could improve the quality of Allii Macrostemonis Bulbus, and it also provided a feasible method for quality evaluation of other traditional Chinese medicines. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Determination of ametoctradin residue in fruits and vegetables by modified quick, easy, cheap, effective, rugged, and safe method using ultra-performance liquid chromatography/tandem mass spectrometry.

    PubMed

    Hu, Mingfeng; Liu, Xingang; Dong, Fengshou; Xu, Jun; Li, Shasha; Xu, Hanqing; Zheng, Yongquan

    2015-05-15

    A rapid, effective and sensitive method to quantitatively determine ametoctradin residue in apple, cucumber, cabbage, tomato and grape was developed and validated using ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). The target compound was determined in less than 5.0 min using an electrospray ionisation source in positive mode (ESI+). The limit of detection was below 0.043 μg kg(-1), whereas the limits of quantification did not exceed 0.135 μg kg(-1) in all five matrices. The method showed excellent linearity (R(2)>0.9969) for the target compound. Recovery studies were performed in all matrices at three spiked levels (1, 10 and 100 μg L(-1)). The mean recoveries from five matrices ranged from 81.81% to 100.1%, with intra-day relative standard deviations (RSDr) in the range of 0.65-7.88% for the test compound. This method will be useful for the quick and routine detection of ametoctradin residues in potato, grape, cucumber, apple and tomato. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Multi-walled carbon nanotubes as solid-phase extraction sorbents for simultaneous determination of type A trichothecenes in maize, wheat and rice by ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Dong, Maofeng; Si, Wenshuai; Jiang, Keqiu; Nie, Dongxia; Wu, Yongjiang; Zhao, Zhihui; De Saeger, Sarah; Han, Zheng

    2015-12-04

    A solid-phase extraction (SPE) procedure using multi-walled carbon nanotubes (MWCNTs) as sorbents coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was developed for simultaneous determination of four type A trichothecenes in maize, wheat and rice for the first time. Several key parameters including the composition of sample loading solutions, washing and elution solvents were thoroughly investigated to achieve optimal SPE recoveries and efficiency. Performance of the MWCNTs materials was significantly affected by pH, and after optimization, n-hexane and 5% methanol aqueous solution as the washing solutions and methanol containing 1% formic acid as the elution solvent presented an excellent purification efficiency for the four targets in the different matrices. The method was validated by determining the linearity (R(2)≥0.992), recovery (73.4-113.7%), precision (1.2-17.1%) and sensitivity (limit of quantification in the range of 0.02-0.10μg/kg), and was further applied for simultaneous determination of type A trichothecenes in 30 samples. Although low contamination levels of type A trichothecenes in wheat, maize and rice were observed revealing mitigated risks to consumers in Shanghai, China, the developed method has proven to be a valuable tool for type A trichothecenes monitoring in complex crop matrices. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Classification of the medicinal plants of the genus Atractylodes using high-performance liquid chromatography with diode array and tandem mass spectrometry detection combined with multivariate statistical analysis.

    PubMed

    Cho, Hyun-Deok; Kim, Unyong; Suh, Joon Hyuk; Eom, Han Young; Kim, Junghyun; Lee, Seul Gi; Choi, Yong Seok; Han, Sang Beom

    2016-04-01

    Analytical methods using high-performance liquid chromatography with diode array and tandem mass spectrometry detection were developed for the discrimination of the rhizomes of four Atractylodes medicinal plants: A. japonica, A. macrocephala, A. chinensis, and A. lancea. A quantitative study was performed, selecting five bioactive components, including atractylenolide I, II, III, eudesma-4(14),7(11)-dien-8-one and atractylodin, on twenty-six Atractylodes samples of various origins. Sample extraction was optimized to sonication with 80% methanol for 40 min at room temperature. High-performance liquid chromatography with diode array detection was established using a C18 column with a water/acetonitrile gradient system at a flow rate of 1.0 mL/min, and the detection wavelength was set at 236 nm. Liquid chromatography with tandem mass spectrometry was applied to certify the reliability of the quantitative results. The developed methods were validated by ensuring specificity, linearity, limit of quantification, accuracy, precision, recovery, robustness, and stability. Results showed that cangzhu contained higher amounts of atractylenolide I and atractylodin than baizhu, and especially atractylodin contents showed the greatest variation between baizhu and cangzhu. Multivariate statistical analysis, such as principal component analysis and hierarchical cluster analysis, were also employed for further classification of the Atractylodes plants. The established method was suitable for quality control of the Atractylodes plants. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Multi-class method for determination of veterinary drug residues and other contaminants in infant formula by ultra performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhan, Jia; Zhong, Ying-ying; Yu, Xue-jun; Peng, Jin-feng; Chen, Shubing; Yin, Ju-yi; Zhang, Jia-Jie; Zhu, Yan

    2013-06-01

    A rapid, simple and generic analytical method which was able to simultaneously determine 220 undesirable chemical residues in infant formula had been developed. The method comprised of extraction with acetonitrile, clean-up by low temperature and water precipitation, and analysis by ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (UPLC-ESI-MS-MS) using multiple reaction monitoring (MRM) mode. Most fat materials in acetonitrile extract were eliminated by low temperature clean-up. The water precipitation, providing a necessary and supplementary cleanup, could avoid losses of hydrophobic analytes (avermectins, ionophores). Average recoveries for spiked infant formula were in the range from 57% to 147% with associated RSD values between 1% and 28%. For over 80% of the analytes, the recoveries were between 70% and 120% with RSD values in the range of 1-15%. The limits of quantification (LOQs) were from 0.01 to 5 μg/kg, which were usually sufficient to verify the compliance of products with legal tolerances. Application of this method in routine monitoring programs would imply a drastic reduction of both effort and time. Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. Wipe selection for the analysis of surface materials containing chemical warfare agent nitrogen mustard degradation products by ultra-high pressure liquid chromatography-tandem mass spectrometry.

    PubMed

    Willison, Stuart A

    2012-12-28

    Degradation products arising from nitrogen mustard chemical warfare agent were deposited on common urban surfaces and determined via surface wiping, wipe extraction, and liquid chromatography–tandem mass spectrometry detection. Wipes investigated included cotton gauze, glass fiber filter, non-woven polyester fiber and filter paper, and surfaces included several porous (vinyl tile, painted drywall, wood) and mostly non-porous (laminate, galvanized steel, glass) surfaces. Wipe extracts were analyzed by ultra-high pressure liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) and compared with high performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS) results. An evaluation of both techniques suggests UPLC–MS/MS provides a quick and sensitive analysis of targeted degradation products in addition to being nearly four times faster than a single HPLC run, allowing for greater throughput during a wide-spread release concerning large-scale contamination and subsequent remediation events. Based on the overall performance of all tested wipes, filter paper wipes were selected over other wipes because they did not contain interferences or native species (TEA and DEA) associated with the target analytes, resulting in high percent recoveries and low background levels during sample analysis. Other wipes, including cotton gauze, would require a pre-cleaning step due to the presence of large quantities of native species or interferences of the targeted analytes. Percent recoveries obtained from a laminate surface were 47–99% for all nitrogen mustard degradation products. The resulting detection limits achieved from wipes were 0.2 ng/cm(2) for triethanolamine (TEA), 0.03 ng/cm(2) for N-ethyldiethanolamine (EDEA), 0.1 ng/cm(2) for N-methyldiethanolamine (MDEA), and 0.1 ng/cm(2) for diethanolamine (DEA).

  18. [High-performance liquid-liquid chromatography in beverage analysis].

    PubMed

    Bricout, J; Koziet, Y; de Carpentrie, B

    1978-01-01

    Liquid liquid chromatography was performed with columns packed with stationary phases chemically bonded to silica microparticules. These columns show a high efficiency and are used very easily. Flavouring compounds like aromatic aldehydes which have a low volatility were analyzed in brandy using a polar phase alkylnitrile. Sapid substances like amarogentin in Gentiana lutea or glyryrrhizin in Glycyrrhiza glabra were determined by reversed phase chromatography. Finally ionizable substances like synthetic dyes can be analyzed by paired ion chromatography witha non polar stationary phase.

  19. Development and validation of an ultra-high performance liquid chromatography-tandem mass spectrometry method to measure creatinine in human urine.

    PubMed

    Fraselle, S; De Cremer, K; Coucke, W; Glorieux, G; Vanmassenhove, J; Schepers, E; Neirynck, N; Van Overmeire, I; Van Loco, J; Van Biesen, W; Vanholder, R

    2015-04-15

    Despite decades of creatinine measurement in biological fluids using a large variety of analytical methods, an accurate determination of this compound remains challenging. Especially with the novel trend to assess biomarkers on large sample sets preserved in biobanks, a simple and fast method that could cope with both a high sample throughput and a low volume of sample is still of interest. In answer to these challenges, a fast and accurate ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed to measure creatinine in small volumes of human urine. In this method, urine samples are simply diluted with a basic mobile phase and injected directly under positive electrospray ionization (ESI) conditions, without further purification steps. The combination of an important diluting factor (10(4) times) due to the use of a very sensitive triple quadrupole mass spectrometer (XEVO TQ) and the addition of creatinine-d3 as internal standard completely eliminates matrix effects coming from the urine. The method was validated in-house in 2012 according to the EMA guideline on bioanalytical method validation using Certified Reference samples from the German External Quality Assessment Scheme (G-Equas) proficiency test. All obtained results for accuracy and recovery are within the authorized tolerance ranges defined by G-Equas. The method is linear between 0 and 5 g/L, with LOD and LOQ of 5 × 10(-3) g/L and 10(-2) g/L, respectively. The repeatability (CV(r) = 1.03-2.07%) and intra-laboratory reproducibility (CV(RW) = 1.97-2.40%) satisfy the EMA 2012 guideline. The validated method was firstly applied to perform the German G-Equas proficiency test rounds 51 and 53, in 2013 and 2014, respectively. The obtained results were again all within the accepted tolerance ranges and very close to the reference values defined by the organizers of the proficiency test scheme, demonstrating an excellent accuracy of the developed method. The

  20. Global chemical profiling based quality evaluation approach of rhubarb using ultra performance liquid chromatography with tandem quadrupole time-of-flight mass spectrometry.

    PubMed

    Zhang, Li; Liu, Haiyu; Qin, Lingling; Zhang, Zhixin; Wang, Qing; Zhang, Qingqing; Lu, Zhiwei; Wei, Shengli; Gao, Xiaoyan; Tu, Pengfei

    2015-02-01

    A global chemical profiling based quality evaluation approach using ultra performance liquid chromatography with tandem quadrupole time-of-flight mass spectrometry was developed for the quality evaluation of three rhubarb species, including Rheum palmatum L., Rheum tanguticum Maxim. ex Balf., and Rheum officinale Baill. Considering that comprehensive detection of chemical components is crucial for the global profile, a systemic column performance evaluation method was developed. Based on this, a Cortecs column was used to acquire the chemical profile, and Chempattern software was employed to conduct similarity evaluation and hierarchical cluster analysis. The results showed R. tanguticum could be differentiated from R. palmatum and R. officinale at the similarity value 0.65, but R. palmatum and R. officinale could not be distinguished effectively. Therefore, a common pattern based on three rhubarb species was developed to conduct the quality evaluation, and the similarity value 0.50 was set as an appropriate threshold to control the quality of rhubarb. A total of 88 common peaks were identified by their accurate mass and fragmentation, and partially verified by reference standards. Through the verification, the newly developed method could be successfully used for evaluating the holistic quality of rhubarb. It would provide a reference for the quality control of other herbal medicines. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. [Direct determination of ethyl carbamate in Chinese rice wine and grape wine by ultra performance liquid chromatography-electrospray ionization tandem mass spectrometry].

    PubMed

    Wang, Lijuan; Ke, Runhui; Wang, Bing; Yin, Jianjun; Song, Quanhou

    2012-09-01

    An ultra performance liquid chromatography-electrospray ionization tandem mass spectrometric (UPLC-ESI-MS/MS) method was established for the direct determination of ethyl carbamate in Chinese rice wine and grape wine. The Chinese rice wine and grape wine samples were diluted with distilled water, filtered through 0. 22 microm microporous membrane. The LC separation was performed on a Waters Acquity UPLC system with a BEH C18 column, acetonitrile and 0. 1% (v/v) acetic acid aqueous solution as the mobile phase. The ethyl carbamate was determined in the mode of electrospray positive ionization (ESI+) and multiple reaction monitoring (MRM). The butyl carbamate (BC) was used as the internal standard for the quantitative determination. The calibration curve showed good linearity in the range of 2 - 500 microg/L with the correlation coefficient greater than 0.995. The limit of detection (LOD) was 1.7 microg/L and the limit of quantification (LOQ) was 5.0 microg/L. The recoveries of the ethyl carbamate in Chinese rice wine and grape wine was in the range of 90% - 102%. The relative standard deviations (RSDs) of intra-day and inter-day determinations were 0. 8% - 4.5% and 1.4% - 5.6% (n = 6). The results indicated that the proposed method is easy, fast, sensitive, and suitable for the determination of ethyl carbamate in Chinese rice wine and grape wine.

  2. Rapid extraction, identification and quantification of drugs of abuse in hair by immunoassay and ultra-performance liquid chromatography tandem mass spectrometry.

    PubMed

    Pichini, Simona; Gottardi, Massimo; Marchei, Emilia; Svaizer, Fiorenza; Pellegrini, Manuela; Rotolo, Maria Concetta; Algar, Oscar García; Pacifici, Roberta

    2014-05-01

    Drug testing in hair is a unique analysis in pharmacotoxicology for establishing a past repeated history of consumption or passive exposure to psychotropic substances. A rather lengthy sample treatment is usually required before parent drugs and eventual metabolites are amenable to quali-quantitative analysis. We evaluated a high throughput screening and confirmation analysis of drugs of abuse in hair by immunoassay and a validated ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) after applying a rapid digestion of the keratin matrix with VMA-T reagent before screening assay and M3 reagent before confirmatory analysis. Samples digestion with VMA-T reagent and immunometric screening analysis of hair calibrators, controls and clinical samples for a total of 150 samples was completed in 4 h. No false-positive and -negative results were found for the control material. UPLC-MS/MS analysis confirmed all of the 31 adult hair samples positive to the screening test using internationally established cut-offs, and identified and quantified drugs of abuse in 32 pediatric hair samples, applying lower limits of quantification from 0.01 to 0.1 ng analyte per mg hair. Analytical recovery was between 70.9% and 100.7%. Intra- and inter-assay imprecision and inaccuracy were always lower than 10%. Rapid extraction, identification and quantification of drugs of abuse in hair by immunoassay and UPLC-MS/MS was tested for its feasibility in clinical samples and provided excellent results for rapid and effective drug testing in hair in epidemiological studies.

  3. Development and validation of an ultra high performance liquid chromatography tandem mass spectrometry method for simultaneous determination of sulfonamides, quinolones and benzimidazoles in bovine milk.

    PubMed

    Hou, Xiao-Lin; Chen, Guo; Zhu, Li; Yang, Ting; Zhao, Jian; Wang, Lei; Wu, Yin-Liang

    2014-07-01

    A simple, sensitive and reliable analytical method was developed for the simultaneous determination of 38 veterinary drugs (18 sulfonamides, 11 quinolones and 9 benzimidazoles) and 8 metabolites of benzimidazoles in bovine milk by ultra high performance liquid chromatography-positive electrospray ionization tandem mass spectrometry (UHPLC-ESI-MS/MS). Samples were extracted with acidified acetonitrile, cleaned up with Oasis(®) MCX cartridges, and analyzed by LC-MS/MS on an Acquity UPLC(®) BEH C18 column with gradient elution. The method allows such multi-analyte measurements within a 13min runtime while the specificity is ensured through the MRM acquisition mode. The method was validated according to the European Commission Decision 2002/657/EC determining specificity, decision limit (CCα), detection capability (CCβ), recovery, precision, linearity and stability. For compounds which have MRLs in bovine milk, the CCα values fall into a range from 11 to 115μg/kg, and the CCβ values fall within a range of 12-125μg/kg. For compounds which have not MRLs in bovine milk, the CCα values fall into a range from 0.01 to 0.08μg/kg, and the CCβ values fall within a range of 0.02-0.11μg/kg. The mean recoveries of the 46 analytes were between 87 and 119%. The calculated RSD values of repeatability and within-laboratory reproducibility experiments were below 11% and 15% for the 46 compounds, respectively. The method was demonstrated to be suitable for the simultaneous determination of sulfonamides, quinolones and benzimidazoles in bovine milk. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Determination of 21 antibiotics in sea cucumber using accelerated solvent extraction with in-cell clean-up coupled to ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhu, Minghua; Zhao, Hongxia; Xia, Deming; Du, Juan; Xie, Huaijun; Chen, Jingwen

    2018-08-30

    An accelerated solvent extraction (ASE) with in-cell clean-up method coupled to ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed to determine 21 antibiotics in sea cucumber. The analytes include 10 sulfonamides, 4 fluoroquinolones, 3 amphenicols, 2 beta-lactams, 1 lincosamide and trimethoprim. Optimal parameters of ASE method were obtained at 80 °C, 1 static cycle of 5 min with methanol/acetonitrile (1/1, v/v) using 2 g of C18 as adsorbent. Recoveries at 50.1-129.2% were achieved with RSD under 20%. Method detection limits ranged from 0.03 to 2.9 μg kg -1 . Compared to the reported ultrasound-assisted extraction method, the proposed method offered comparable extraction efficiency for sulfonamides from sea cucumber, but higher for other categories of antibiotics. This validated method was then successfully applied to sea cucumber samples and 9 antibiotics were detected with the highest concentration up to 57.7 μg kg -1 for norfloxacin. Copyright © 2018 Elsevier Ltd. All rights reserved.

  5. An on-spot internal standard addition approach for accurately determining colistin A and colistin B in dried blood spots using ultra high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Tsai, I-Lin; Kuo, Ching-Hua; Sun, Hsin-Yun; Chuang, Yu-Chung; Chepyala, Divyabharathi; Lin, Shu-Wen; Tsai, Yun-Jung

    2017-10-25

    Outbreaks of multidrug-resistant Gram-negative bacterial infections have been reported worldwide. Colistin, an antibiotic with known nephrotoxicity and neurotoxicity, is now being used to treat multidrug-resistant Gram-negative strains. In this study, we applied an on-spot internal standard addition approach coupled with an ultra high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) method to quantify colistin A and B from dried blood spots (DBSs). Only 15μL of whole blood was required for each sample. An internal standard with the same yield of extraction recoveries as colistin was added to the spot before sample extraction for accurate quantification. Formic acid in water (0.15%) with an equal volume of acetonitrile (50:50v/v) was used as the extraction solution. With the optimized extraction process and LC-MS/MS conditions, colistin A and B could be quantified from a DBS with respective limits of quantification of 0.13 and 0.27μgmL -1 , and the retention times were < 2min. The relative standard deviations of within-run and between-run precisions for peak area ratios were all < 17.3%. Accuracies were 91.5-111.2% for lower limit of quantification, low, medium, and high QC samples. The stability of the easily hydrolyzed prodrug, colistin methanesulfonate, was investigated in DBSs. Less than 4% of the prodrug was found to be hydrolyzed in DBSs at room temperature after 48h. The developed method applied an on-spot internal standard addition approach which benefited the precision and accuracy. Results showed that DBS sampling coupled with the sensitive LC-MS/MS method has the potential to be an alternative approach for colistin quantification, where the bias of prodrug hydrolysis in liquid samples is decreased. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Rapid determination of some beta-blockers in complicated matrices by tandem dispersive liquid-liquid microextraction followed by high performance liquid chromatography.

    PubMed

    Hemmati, Maryam; Asghari, Alireza; Bazregar, Mohammad; Rajabi, Maryam

    2016-11-01

    In this research work, an efficient tandem dispersive liquid-liquid microextraction (TDLLME) procedure coupled with high performance liquid chromatography-ultraviolet detection (HPLC-UV) was successfully applied for the determination of beta-blockers in human plasma and pharmaceutical wastewater samples. High clean-up and preconcentration factor are easily and rapidly feasible via this novel, cheap, and safe microextraction method, leading to high quality experimental data. It consists of two sequential dispersive liquid-liquid microextraction methods, accomplished via air/ultrasonic agitation and air agitation, respectively. In order to enrich the optimal values for the mentioned procedures, the Box-Behnken design (BBD) combined with the desirability function (DF) was used. The optimum values were found to be 11.0 % (w/v) of the salt amount, an initial pH value of 12.0, 103 μL of organic extractant phase, and 45 μL of aqueous extractant phase with pH value of 2.0, resulted in reasonable recovery percentages with a logical desirability. Under optimal experimental conditions, good linear ranges (3-2000 ng mL -1 for metoprolol and 2.5-2500 ng mL -1 for propranolol with the correlation of determinations (R 2 s) higher than 0.99) and low limits of detection (0.8 and 1.0 ng mL -1 for propranolol and metoprolol, respectively) were obtainable. Also, TDLLME-HPLC-UV provided good proper repeatabilities (relative standard deviations (RSDs) below 5.7 %, n = 3) and high enrichment factors (EFs) of 75-100. Graphical abstract TDLLME of beta-blockers from complicated matrices.

  7. Simultaneous quantification of four metabolites of sulfur mustard in urine samples by ultra-high performance liquid chromatography-tandem mass spectrometry after solid phase extraction.

    PubMed

    Liu, Chang-Cai; Liu, Shi-Lei; Xi, Hai-Ling; Yu, Hui-Lan; Zhou, Shi-Kun; Huang, Gui-Lan; Liang, Long-Hui; Liu, Jing-Quan

    2017-04-07

    Four HD urinary metabolites including hydrolysis metabolite thiodiglycol (TDG), glutathione-derived metabolite 1,1'-sulfonylbis[2-S-(N-acetylcysteinyl)ethane] (SBSNAE), as well as the β-lyase metabolites 1,1'-sulfonylbis[2-(methylsulfinyl)ethane] (SBMSE) and 1-methylsulfinyl-2-[2-(methylthio) ethylsulfonyl]ethane (MSMTESE) are considered as important biomarkers for short-term retrospective detection of HD exposure. In this study, a single method for simultaneous quantification of the four HD metabolites in urine samples was developed using ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The four urinary metabolites were simultaneously extracted from urinary samples using a solid phase extraction (SPE) method with high extraction recoveries for all four metabolites varied in the range of 71.1-103% followed by UHPLC-MS/MS analysis. The SPE is simple and high effective only requiring 0.1mL of urinary samples and 0.5h time consuming. The problem of previous co-elution of TDG and SBSNAE in UHPLC was well solved, and complete separation of TDG, SBSNAE, SBMSE and MSMTESE from SPE-processed urine matrix was obtained to increase specificity and sensitivity. A full method validation was performed for each analyte in urine matrix. The linear range of calibration curves for the four analytes were respectively from 0.50-500ngmL -1 for TDG and SBSNAE, 0.05-500ngmL -1 for SBMSE and MSMTESE with coefficient of determination value (R 2 ) ≥0.990. The limit of detection was 0.25ngmL -1 for TDG and SBSNAE, 0.01ngmL -1 for SBMSE and MSMTESE spiked in normal urine. The intra/inter-day precision for each analyte at three QC levels had relative standard deviation (%RSD) of ≤10.3%, and the intra/inter-day accuracy ranged between 88.0-108%. This developed method allows for simultaneous and trace measurement of four HD urinary metabolites within one single determination with the lowest usage amount of urine samples over all previous methods This

  8. Analysis of glycosaminoglycans in cerebrospinal fluid from patients with mucopolysaccharidoses by isotope-dilution ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhang, Haoyue; Young, Sarah P; Auray-Blais, Christiane; Orchard, Paul J; Tolar, Jakub; Millington, David S

    2011-07-01

    New therapies for the treatment of mucopolysaccharidoses that target the brain, including intrathecal enzyme replacement, are being explored. Quantitative analysis of the glycosaminoglycans (GAGs) that accumulate in these disorders is required to assess the disease burden and monitor the effect of therapy in affected patients. Because current methods lack the required limit of quantification and specificity to analyze GAGs in small volumes of cerebrospinal fluid (CSF), we developed a method based on ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Samples of CSF (25 μL) were evaporated to dryness and subjected to methanolysis. The GAGs were degraded to uronic acid-N-acetylhexosamine dimers and mixed with internal standards derived from deuteriomethanolysis of GAG standards. Specific dimers derived from heparan, dermatan and chondroitin sulfates (HS, DS and CS) were separated by UPLC and analyzed by electrospray ionization MS/MS using selected reaction monitoring for each targeted GAG product and its corresponding internal standard. CSF from control pediatric subjects (n = 22) contained <0.38 mg/L HS, 0.26 mg/L DS, and 2.8 mg/L CS, whereas CSF from patients with Hurler syndrome (n = 7) contained concentrations of DS and HS that were at least 6-fold greater than the upper control limits. These concentrations were reduced by 17.5% to 82.5% after allogeneic transplantation and treatment with intrathecal and intravenous enzyme replacement therapy. The method described here has potential value in monitoring patients with mucopolysaccharidoses receiving treatment targeted to the brain.

  9. Qualitative and Quantitative Analysis of Volatile Components of Zhengtian Pills Using Gas Chromatography Mass Spectrometry and Ultra-High Performance Liquid Chromatography.

    PubMed

    Liu, Cui-Ting; Zhang, Min; Yan, Ping; Liu, Hai-Chan; Liu, Xing-Yun; Zhan, Ruo-Ting

    2016-01-01

    Zhengtian pills (ZTPs) are traditional Chinese medicine (TCM) which have been commonly used to treat headaches. Volatile components of ZTPs extracted by ethyl acetate with an ultrasonic method were analyzed by gas chromatography mass spectrometry (GC-MS). Twenty-two components were identified, accounting for 78.884% of the total components of volatile oil. The three main volatile components including protocatechuic acid, ferulic acid, and ligustilide were simultaneously determined using ultra-high performance liquid chromatography coupled with diode array detection (UHPLC-DAD). Baseline separation was achieved on an XB-C18 column with linear gradient elution of methanol-0.2% acetic acid aqueous solution. The UHPLC-DAD method provided good linearity (R (2) ≥ 0.9992), precision (RSD < 3%), accuracy (100.68-102.69%), and robustness. The UHPLC-DAD/GC-MS method was successfully utilized to analyze volatile components, protocatechuic acid, ferulic acid, and ligustilide, in 13 batches of ZTPs, which is suitable for discrimination and quality assessment of ZTPs.

  10. Simultaneous quantification of four antiretroviral drugs in breast milk samples from HIV-positive women by an ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method

    PubMed Central

    Rodríguez-Delgado, Rosa Georgina; Figueroa-Damián, Ricardo; Domínguez-Castro, Mauricio; López-Martínez, Margarita; Flores-García, Zayra

    2018-01-01

    The primary strategy to avoid mother-to-child transmission of human immunodeficiency virus (HIV) through breastfeeding is administration of highly active antiretroviral therapy (HAART) to HIV-positive pregnant women. Because significant changes in the pharmacokinetics of antiretroviral (ARV) drugs occur during pregnancy, quantifying HAART and the viral load in breast milk in this population is essential. Here, we developed an analytical assay for the simultaneous quantification of four ARV drugs in breast milk using ultra-performance liquid chromatography coupled to tandem mass spectrometry. We validated this method following Mexican and international guidelines. ARV drugs. We extracted the ARV drugs from 200 μL samples of breast milk and detected these drugs in a triple quadrupole mass spectrometer with positive electrospray ionization. The validated concentration ranges (ng/mL) for zidovudine, lamivudine, lopinavir, and ritonavir were 12.5–750, 50–2500, 100–5000 and 5 to 250, respectively. Additionally, the absolute recovery percentages (and matrix effects) were 91.4 (8.39), 88.78 (28.75), 91.38 (11.77) and 89.78 (12.37), respectively. We determined that ARV drugs are stable for 24 h at 8°C and 24°C for 15 days at –80°C. This methodology had the capacity for simultaneous detection; separation; and accurate, precise quantification of ARV drugs in human breast milk samples according to Mexican standard laws and United States Food and Drug Administration guidelines. PMID:29351333

  11. Development and validation of a streamlined method designed to detect residues of 62 veterinary drugs in bovine kidney using ultra-high performance liquid chromatography--tandem mass spectrometry.

    PubMed

    Lehotay, Steven J; Lightfield, Alan R; Geis-Asteggiante, Lucía; Schneider, Marilyn J; Dutko, Terry; Ng, Chilton; Bluhm, Louis; Mastovska, Katerina

    2012-08-01

    In the USA, the US Department of Agriculture's Food Safety and Inspection Service (FSIS) conducts the National Residue Program designed to monitor veterinary drug and other chemical residues in beef and other slaughtered food animals. Currently, FSIS uses a 7-plate bioassay in the laboratory to screen for antimicrobial drugs in bovine kidneys from those animals tested positive by inspectors in the slaughter establishments. The microbial inhibition bioassay has several limitations in terms of monitoring scope, sensitivity, selectivity, and analysis time. Ultra-high performance liquid chromatography - tandem mass spectrometry (UHPLC-MS/MS) has many advantages over the bioassay for this application, and this study was designed to develop, evaluate, and validate a fast UHPLC-MS/MS method for antibiotics and other high-priority veterinary drugs in bovine kidney. Five existing multi-class, multi-residue methods from the literature were tested and compared, and each performed similarly. Experiments with incurred samples demonstrated that a 5-min shake of 2 g homogenized kidney with 10 ml of 4/1 (v/v) acetonitrile/water followed by simultaneous clean-up of the initial extract with 0.5 g C18 and 10 ml hexane gave a fast, simple, and effective sample preparation method for the <10 min UHPLC-MS/MS analysis. An extensive 5-day validation process demonstrated that the final method could be used to acceptably screen for 54 of the 62 drugs tested, and 50 of those met qualitative MS identification criteria. Quantification was not needed in the application, but the method gave ≥ 70% recoveries and ≤ 25% reproducibilities for 30 of the drugs. Published 2012. This article is a U.S. Government work and is in the public domain of the USA.

  12. Air-assisted liquid-liquid microextraction integrated with QuEChERS for determining endocrine-disrupting compounds in fish by high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Luo, Zhoufei; Lu, Jing; Li, Haipu; Tu, Yi; Wan, Yuehao; Yang, Zhaoguang

    2018-09-15

    A new, sensitive, and rapid method based on the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) approach and air-assisted liquid-liquid microextraction (AALLME) technology was developed for the determination of 20 endocrine-disrupting compounds (EDCs) in fish by high-performance liquid chromatography-tandem mass spectrometry. The method first integrates AALLME into QuEChERS to achieve clean-up and enrichment of the EDCs in one step. A self-made glass tube was enfolded with plasticine to withstand the high centrifugal force. The established method was developed by optimization of the parameters. High linearities (R 2  > 0.9924) and recoveries (78.2-118.6%) at three spiked levels (5, 10, and 20 ng g -1 ), and low relative standard deviation values (1.1-14.5%) and limits of detection (0.03-0.80 ng g -1 ) were obtained. The method comparison shows that the proposed method is superior as it involves less organic solvent usage, simple operation and high efficiency. This method was successfully applied to different fishes for analyzing EDCs. Copyright © 2018 Elsevier Ltd. All rights reserved.

  13. Screening approach by ultra-high performance liquid chromatography-tandem mass spectrometry for the blood quantification of thirty-four toxic principles of plant origin. Application to forensic toxicology.

    PubMed

    Carlier, Jérémy; Guitton, Jérôme; Romeuf, Ludovic; Bévalot, Fabien; Boyer, Baptiste; Fanton, Laurent; Gaillard, Yvan

    2015-01-15

    Plant poisonings have left their mark on history and still cause many deaths, whether intentional or accidental. The means to show toxicological evidence of such poisonings should be implemented with great care. This article presents a technique for measuring thirty-nine toxic principles of plant origin in the blood, covering a large amount of toxins from local or exotic plants: α-lobeline, α-solanine, aconitine, ajmaline, atropine, brucine, cephalomannine, colchicine, convallatoxin, cymarine, cytisine, digitoxin, digoxin, emetine, gelsemine, ibogaine, jervine, kavain, lanatoside C, lupanine, mitragynine, neriifolin, oleandrin, ouabain, paclitaxel, physostigmine, pilocarpine, podophyllotoxin, proscillaridin A, reserpine, retrorsine, ricinine, scopolamine, senecionine, sparteine, strophanthidin, strychnine, veratridine and yohimbine. Analysis was carried out using an original ultra-high performance liquid chromatography separation coupled with tandem mass spectrometry detection. Extraction was a standard solid phase extraction performed on Oasis(®) HLB cartridge. Thirty-four of the thirty-nine compounds were put through a validation procedure. The assay was linear in the calibration curve range from 0.5 or 5 μg/L to 1000 μg/L according to the compounds. The method is sensitive (LOD from 0.1 to 1.6 μg/L). The within-day precision of the assay was less than 22.5% at the LLOQ, and the between-day precision was less than 21.5% for 10 μg/L for all the compounds included. The assay accuracy was in the range of 87.4 to 119.8% for the LLOQ. The extraction recovery and matrix effect ranged from 30 to 106% and from -30 to 14%, respectively. It has proven useful and effective in several difficult forensic cases. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Liquid chromatography and supercritical fluid chromatography as alternative techniques to gas chromatography for the rapid screening of anabolic agents in urine.

    PubMed

    Desfontaine, Vincent; Nováková, Lucie; Ponzetto, Federico; Nicoli, Raul; Saugy, Martial; Veuthey, Jean-Luc; Guillarme, Davy

    2016-06-17

    This work describes the development of two methods involving supported liquid extraction (SLE) sample treatment followed by ultra-high performance liquid chromatography or ultra-high performance supercritical fluid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS and UHPSFC-MS/MS) for the screening of 43 anabolic agents in human urine. After evaluating different stationary phases, a polar-embedded C18 and a diol columns were selected for UHPLC-MS/MS and UHPSFC-MS/MS, respectively. Sample preparation, mobile phases and MS conditions were also finely tuned to achieve highest selectivity, chromatographic resolution and sensitivity. Then, the performance of these two methods was compared to the reference routine procedure for steroid analyses in anti-doping laboratories, which combines liquid-liquid extraction (LLE) followed by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). For this purpose, urine samples spiked with the compounds of interest at five different concentrations were analyzed using the three analytical platforms. The retention and selectivity of the three techniques were very different, ensuring a good complementarity. However, the two new methods displayed numerous advantages. The overall procedure was much faster thanks to high throughput SLE sample treatment using 48-well plates and faster chromatographic analysis. Moreover, the highest sensitivity was attained using UHPLC-MS/MS with 98% of the doping agents detected at the lowest concentration level (0.1ng/mL), against 76% for UHPSFC-MS/MS and only 14% for GC-MS/MS. Finally, the weakest matrix effects were obtained with UHPSFC-MS/MS with 76% of the analytes displaying relative matrix effect between -20 and 20%, while the GC-MS/MS reference method displayed very strong matrix effects (over 100%) for all of the anabolic agents. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Determination of fluorotelomer alcohols and their degradation products in biosolids-amended soils and plants using ultra-high performance liquid chromatography tandem mass spectrometry.

    PubMed

    Zhang, Hongna; Wen, Bei; Hu, Xiaoyu; Wu, Yali; Luo, Lei; Chen, Zien; Zhang, Shuzhen

    2015-07-24

    Degradation of fluorotelomer alcohols (FTOHs) was recognized as an additional source of perfluorocarboxylic acids (PFCAs). Quantification of FTOHs and their degradation products can help shed light on the sources and fates of PFCAs in the environment. In this study, an analytical method was developed for the determination of 6:2 and 8:2 FTOHs, and their degradation products of poly- and perfluorinated acids, including fluorotelomer saturated and unsaturated carboxylic acids (FTCAs and FTUCAs), secondary polyfluorinated alcohols and PFCAs in biosolids-amended soils and plants using ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). The extract efficiencies of different methods including ethyl acetate and methanol (MeOH) for FTOHs and acetonitrile, MeOH, methyl tert-butyl ether (MTBE), NaOH-MeOH and NaOH-MTBE for poly- and perfluorinated acids were tested. The results showed that 6:2 and 8:2 FTOHs and their degradation products could be simultaneously and satisfactorily extracted by MeOH, cleaned up by Envi-Carb graphitized carbon and solid phase extraction, respectively, and determined by UPLC-MS/MS separately. NaOH in the extractant caused the conversion of 6:2 FTCA and 8:2 FTCA into the corresponding FTUCAs. The selected methods have matrix recoveries ranged from 52% to 102%, and detection limits of 0.01-0.46ng/g dry weight for FTOHs and their degradation products in soil and plant. The optimized method was applied successfully to quantify FTOHs and their degradation products in two biosolids-amended soils and plants. The total concentrations of FTOHs in the soils were 44.1±5.8 and 82.6±7.1ng/g, and in plants tissues 3.58±0.25 and 8.33±0.66ng/g. The total concentrations of poly- and perfluorinated acids in the soils were 168.0±13.2 and 349.6±11.2ng/g, and in plants tissues 78.0±6.4 and 75.5±5.3ng/g. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Simultaneous analysis of different classes of phytohormones in coconut (Cocos nucifera L.) water using high-performance liquid chromatography and liquid chromatography-tandem mass spectrometry after solid-phase extraction.

    PubMed

    Ma, Zhen; Ge, Liya; Lee, Anna S Y; Yong, Jean Wan Hong; Tan, Swee Ngin; Ong, Eng Shi

    2008-03-10

    Coconut (Cocos nucifera L.) water, which contains many uncharacterized phytohormones is extensively used as a growth promoting supplement in plant tissue culture. In this paper, a high-performance liquid chromatography (HPLC) method was developed for the simultaneous determination of various classes phytohormones, including indole-3-acetic acid (IAA), indole-3-butyric acid (IBA), abscisic acid (ABA), gibberellic acid (GA), zeatin (Z), N(6)-benzyladenine (BA), alpha-naphthaleneacetic acid (NAA) and 2,4-dichlorophenoxyacetic acid (2,4-D) in young coconut water (CW). The analysis was carried out using a reverse-phase HPLC gradient elution, with an aqueous mobile phase (containing 0.1% formic acid, pH adjusted to 3.2 with triethylamine (TEA)) modified by methanol, and solute detection made at 265 nm wavelength. The method was validated for specificity, quantification, accuracy and precision. After preconcentration of putative endogenous phytohormones in CW using C(18) solid-phase extraction (SPE) cartridges, the HPLC method was able to screen for putative endogenous phytohormones present in CW. Finally, the identities of the putative phytohormones present in CW were further confirmed using independent liquid chromatography-tandem mass spectrometry (LC-MS/MS) equipped with an electrospray ionization (ESI) interface.

  17. Sensitive analysis of steroid estrogens and bisphenol a in small volumes of water using isotope-dilution ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Chang, Hong; Shen, Xiaoyan; Shao, Bing; Wu, Fengchang

    2018-04-01

    An isotope-dilution ultra-performance liquid chromatography-electrospray tandem mass spectrometry method combined with dansylation was established to sensitively quantify four steroid estrogens (estrone, 17α-estradiol, 17β-estradiol and 17α-ethynylestradiol) and bisphenol A in sewage influent and effluent. A simple hexane extraction was performed from a small volume (10 mL), followed by dansyl chloride derivatization and purification with a silica cartridge. The method effectively reduced the matrix effects in sample extract and permitted the selective and sensitive determination of target compounds from complicated matrices. The detection limits of the method for steroid estrogens were 0.20-0.90 ng L -1 in influent and 0.10-0.20 ng L -1 in effluent samples. For bisphenol A, the limits detection of the method were 20 and 0.80 for influent and effluent samples, respectively. Recoveries of 85%-96% were observed in all matrices. The method was applied to analyze residual estrogens and bisphenol A in sewage influent and effluent samples from Beijing, China. The concentrations of bisphenol A (636-1200 ng L -1 ) were up to 250 times higher than those of steroid estrogens. Estrone was the dominant estrogen in influent and effluent samples, while similar concentrations of 17α-estradiol and 17β-estradiol were detected in all samples. Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. A fully automated method for simultaneous determination of aflatoxins and ochratoxin A in dried fruits by pressurized liquid extraction and online solid-phase extraction cleanup coupled to ultra-high-pressure liquid chromatography-tandem mass spectrometry.

    PubMed

    Campone, Luca; Piccinelli, Anna Lisa; Celano, Rita; Russo, Mariateresa; Valdés, Alberto; Ibáñez, Clara; Rastrelli, Luca

    2015-04-01

    According to current demands and future perspectives in food safety, this study reports a fast and fully automated analytical method for the simultaneous analysis of the mycotoxins with high toxicity and wide spread, aflatoxins (AFs) and ochratoxin A (OTA) in dried fruits, a high-risk foodstuff. The method is based on pressurized liquid extraction (PLE), with aqueous methanol (30%) at 110 °C, of the slurried dried fruit and online solid-phase extraction (online SPE) cleanup of the PLE extracts with a C18 cartridge. The purified sample was directly analysed by ultra-high-pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) for sensitive and selective determination of AFs and OTA. The proposed analytical procedure was validated for different dried fruits (vine fruit, fig and apricot), providing method detection and quantification limits much lower than the AFs and OTA maximum levels imposed by EU regulation in dried fruit for direct human consumption. Also, recoveries (83-103%) and repeatability (RSD < 8, n = 3) meet the performance criteria required by EU regulation for the determination of the levels of mycotoxins in foodstuffs. The main advantage of the proposed method is full automation of the whole analytical procedure that reduces the time and cost of the analysis, sample manipulation and solvent consumption, enabling high-throughput analysis and highly accurate and precise results.

  19. Rapid determination of phenolic compounds and alkaloids of carob flour by improved liquid chromatography tandem mass spectrometry.

    PubMed

    Ortega, Nàdia; Macià, Alba; Romero, Maria-Paz; Trullols, Esther; Morello, Jose-Ramón; Anglès, Neus; Motilva, Maria-Jose

    2009-08-26

    An improved chromatographic method was developed using ultra-performance liquid chromatography-tandem mass spectrometry to identify and quantify phenolic compounds and alkaloids, theobromine and caffeine, in carob flour samples. The developed method has been validated in terms of speed, sensitivity, selectivity, peak efficiency, linearity, reproducibility, limits of detection, and limits of quantification. The chromatographic method allows the identification and quantification of 20 phenolic compounds, that is, phenolic acids, flavonoids, and their aglycone and glucoside forms, together with the determination of the alkaloids, caffeine and theobromine, at low concentration levels all in a short analysis time of less than 20 min.

  20. High-performance Liquid Chromatographic Ultraviolet Detection of Nilotinib in Human Plasma from Patients with Chronic Myelogenous Leukemia, and Comparison with Liquid Chromatography-Tandem Mass Spectrometry.

    PubMed

    Nakahara, Ryosuke; Satho, Yuhki; Itoh, Hiroki

    2016-11-01

    A method for determining nilotinib concentration in human plasma is proposed using high-performance liquid chromatography and ultraviolet detection. Nilotinib and the internal standard dasatinib were separated using a mobile phase of 0.5% Na 2 PO 4 H 2 O (pH 2.5)-acetonitrile-methanol (55:25:20, v/v/v) on a Capcell Pak C18 MG II column (250 × 4.6 mm) at a flow rate of 1.0 ml/min, and ultraviolet measurement at 250 nm. The calibration curve exhibited linearity over the nilotinib concentration range of 50-2,500 ng/ml at 250 nm, with relative standard deviations (n = 5) of 7.1%, 2.5%, and 2.9% for 250, 1,500, and 2,500 ng/ml, respectively. The detection limit for nilotinib was 5 ng/ml due to three blank determinations (ρ = 3). This method was successfully applied to assaying nilotinib in human plasma samples from patients with chronic myelogenous leukemia. In addition, we compared the results with those measured by liquid chromatography-tandem mass spectrometry (LC-MS/MS) at BML, Inc. (a commercial laboratory). A strong correlation was observed between the nilotinib concentrations measured by our high-performance liquid chromatographic method and those obtained by LC/MS-MS (r 2 = 0.988, P < 0.01). © 2016 Wiley Periodicals, Inc.

  1. Identification and quantification of 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid glucuronide (THC-COOH-glu) in hair by ultra-performance liquid chromatography tandem mass spectrometry as a potential hair biomarker of cannabis use.

    PubMed

    Pichini, Simona; Marchei, Emilia; Martello, Simona; Gottardi, Massimo; Pellegrini, Manuela; Svaizer, Fiorenza; Lotti, Andrea; Chiarotti, Marcello; Pacifici, Roberta

    2015-04-01

    We developed and validated an ultra-high-pressure liquid chromatography-tandem mass spectrometry method to identify and quantify 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid glucuronide in hair of cannabis consumers. After hair washing with methyl alcohol and diethyl ether and subsequent addition of amiodarone as internal standard hair samples were treated with 500 μl VMA-T M3 buffer reagent for 1 h at 100 °C. After cooling, 10 μl VMA-T M3 extract were injected into chromatographic system. Chromatographic separation was carried out on a reversed phase column using a linear gradient elution with two solvents: 5 mM ammonium formate pH 3.0 (solvent A) and 0.1% formic acid in acetonitrile (solvent B). The flow rate was kept constant at 0.4 ml/min during the analysis. The separated analytes were detected with a triple quadrupole mass spectrometer operated in multiple reaction monitoring mode via positive electrospray ionization. Linear calibration curves were obtained for 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid glucuronide with correlation coefficients (r(2)) of 0.99 and a limit of quantification of 0.25 pg/mg hair. Analytical recovery was between 79.6% and 100.7% and intra- and inter-assay imprecision and inaccuracy were always lower than 15%. Ultra-high-pressure liquid chromatography-tandem mass spectrometry analysis of 20 different hair samples of cannabis consumers disclosed the presence of 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid glucuronide in the range of 0.5-8.6 pg/mg hair. These data provided a good start to consider 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid glucuronide as alternative hair biomarker of cannabis consumption. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  2. Application of Ultra-performance Liquid Chromatography with Time-of-Flight Mass Spectrometry for the Rapid Analysis of Constituents and Metabolites from the Extracts of Acanthopanax senticosus Harms Leaf

    PubMed Central

    Zhang, Yingzhi; Zhang, Aihua; Zhang, Ying; Sun, Hui; Meng, Xiangcai; Yan, Guangli; Wang, Xijun

    2016-01-01

    Acanthopanax senticosus (Rupr and Maxim) Harms (AS), a member of Araliaceae family, is a typical folk medicinal herb, which is widely distributed in the Northeastern part of China. Due to lack of this resource caused by the extensive use of its root, this work studied the chemical constituents of leaves of this plant with the purpose of looking for an alternative resource. In this work, a fast and optimized ultra-performance liquid chromatography method with quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS) has been developed for the analysis of constituents in leaves extracts. A total of 131 compounds were identified or tentatively characterized including triterpenoid saponins, phenols, flavonoids, lignans, coumarins, polysaccharides, and other compounds based on their fragmentation behaviors. Besides, a total of 21 metabolites were identified in serum in rats after oral administration, among which 12 prototypes and 9 metabolites through the metabolic pathways of reduction, methylation, sulfate conjugation, sulfoxide to thioether and deglycosylation. The coupling of UPLC-QTOF-MS led to the in-depth characterization of the leaves extracts of AS both in vitro and in vivo on the basis of retention time, mass accuracy, and tandem MS/MS spectra. It concluded that this analytical tool was very valuable in the study of complex compounds in medicinal herb. HIGHLIGHT OF PAPER A fast UPLC-QTOF-MS has been developed for analysis of constituents in leaves extractsA total of 131 compounds were identified in leaves extractsA total of 21 metabolites including 12 prototypes and 9 metabolites were identified in vivo. SUMMARY Constituent’s analysis of Acanthopanax senticosus Harms leaf by ultra-performance liquid chromatography method with quadrupole time-of-flight mass spectrometry. Abbreviations used: AS: Acanthopanax senticosus (Rupr and Maxim) Harms, TCHM: Traditional Chinese herbal medicine, UPLC-QTOF-MS: Ultra-performance liquid chromatography method with time

  3. Urinary metabolomic study of non-small cell lung carcinoma based on ultra high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry.

    PubMed

    Wu, Qian; Wang, Yan; Gu, Xue; Zhou, Junyi; Zhang, Huiping; Lv, Wang; Chen, Zhe; Yan, Chao

    2014-07-01

    Metabolic profiles from human urine reveal the significant difference of carnitine and acylcarnitines levels between non-small cell lung carcinoma patients and healthy controls. Urine samples from cancer patients and healthy individuals were assayed in this metabolomic study using ultra high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry. The data were normalized by the sum of all intensities and creatinine calibration, respectively, before orthogonal partial least squares discriminant analysis. Twenty differential metabolites were identified based on standard compounds or tandem mass spectrometry fragments. Among them, some medium-/long-chain acylcarnitines, for example, cis-3,4-methylene heptanoylcarnitine, were found to be downregulated while carnitine was upregulated in urine samples from the cancer group compared to the control group. Receiver operating characteristic analysis of the two groups showed that the area under curve for the combination of carnitine and 11 selected acylcarnitines was 0.958. This study suggests that the developed carnitine and acylcarnitines profiling method has the potential to be used for screening non-small cell lung carcinoma. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Enantioselective ultra high performance liquid and supercritical fluid chromatography: The race to the shortest chromatogram.

    PubMed

    Ciogli, Alessia; Ismail, Omar H; Mazzoccanti, Giulia; Villani, Claudio; Gasparrini, Francesco

    2018-03-01

    The ever-increasing need for enantiomerically pure chiral compounds has greatly expanded the number of enantioselective separation methods available for the precise and accurate measurements of the enantiomeric purity. The introduction of chiral stationary phases for liquid chromatography in the last decades has revolutionized the routine methods to determine enantiomeric purity of chiral drugs, agrochemicals, fragrances, and in general of organic and organometallic compounds. In recent years, additional efforts have been placed on faster, enantioselective analytical methods capable to fulfill the high throughput requirements of modern screening procedures. Efforts in this field, capitalizing on improved chromatographic particle technology and dedicated instrumentation, have led to highly efficient separations that are routinely completed on the seconds time scale. An overview of the recent achievements in the field of ultra-high-resolution chromatography on column packed with chiral stationary phases, both based on sub-2 μm fully porous and sub-3 μm superficially porous particles, will be given, with an emphasis on very recent studies on ultrafast chiral separations. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. [Simultaneous determination of ten benzotriazole ultraviolet stabilizers in food contact plastic materials by solid phase extraction and ultra performance liquid chromatography with tandem mass spectrometry].

    PubMed

    Gou, Xinlei; Zhao, Xinying; Chi, Haitao; Gao, Xia; Zhou, Mingqiang; Liu, Weili

    2015-06-01

    A sensitive method was developed for the simultaneous determination of ten benzotriazole ultraviolet stabilizers in food contact plastic materials by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The sample was extracted by methanol-dichloromethane, and purified by a C18 solid-phase extraction (SPE) column. The separation was performed by using water containing 0. 1% (v/v) formic acid and methanol as the mobile phases with gradient elution at a flow rate of 0. 3 mL/min. The electrospray ionization (ESI) source in positive ion mode was used for the analysis of the ten benzotriazole ultraviolet stabilizers in multiple reaction monitoring (MRM) mode. The results showed that the standard curves were obtained with good correlation coefficients (r2 > 0.996) in their linear concentration ranges. The limits of detection (LODs, S/N = 3) for the ten benzotriazole ultraviolet stabilizers were in the range of 0.6-1.6 µg/kg. The mean recoveries for the ten benzotriazole ultraviolet stabilizers at three spiked levels (low, medium and high) were 75.2%-85.3% with relative standard deviations of 1.0%-5.7%. Ten kinds of food contact plastic materials were tested, and 2,2'-methylenebis (6-(benzotriazol-2-yl)-4-tert-octylphenol) (UV-360) was found in a sample of polyethylene (PE) material. The method is accurate, simple, rapid and feasible for the simultaneous determination of benzotriazole ultraviolet stabilizers in food plastic materials.

  6. Determination of aflatoxins in medicinal plants by high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Siddique, Nadeem A; Mujeeb, Mohd; Ahmad, Sayeed; Panda, Bibhu P; Makhmoor, Mohd

    2013-01-01

    The intention of the proposed work is to study the presence of the aflatoxins B1, B2, G1 and G2 in medicinal plants, namely Mucuna pruriens, Delphinium denudatum and Portulaca oleraceae. The aflatoxins were extracted, purified by immunoaffinity column chromatography and analysed by high-performance liquid chromatography-tandem quadrupole mass spectrometry with electrospray ionisation (HPLC-MS/MS). Fungal count was carried out in PDA media. A good linear relationship was found for AFB1, AFB2, AFG1 and AFG2 at 1-10 ppb (r>0.9995). The analyte accuracy under three different spiking levels was 86.7-108.1 %, with low per cent relative standard deviations in each case. The aflatoxins can be separated within 5 to7 min using an Agilent XDB C18-column. We found that AFB1 and AFB2 were in trace amounts below the detection limit in M. pruriens whilst they were not detected in D. denudatum. P. oleraceae was found to be contaminated with AFB1 and AFB2. AFG1 and AFG2 were not detected in M. pruriens, P. oleraceae and were below the detection limit in D. denudatum. This was consistent with very low numbers of fungal colonies observed after 6 hr of incubation. The analytical method developed is simple, precise, accurate, economical and can be effectively used to determine the aflatoxins in medicinal plants and therefore to control the quality of products. The aflatoxin levels in the plant extracts examined were related to the minimal fungal load in the medicinal plants examined.

  7. Metabolic Profile of Skimmianine in Rats Determined by Ultra-Performance Liquid Chromatography Coupled with Quadrupole Time-of-Flight Tandem Mass Spectrometry.

    PubMed

    Huang, Aihua; Xu, Hui; Zhan, Ruoting; Chen, Weiwen; Liu, Jiawei; Chi, Yuguang; Chen, Daidi; Ji, Xiaoyu; Luo, Chaoquan

    2017-03-23

    Skimmianine is a furoquinoline alkaloid present mainly in the Rutaceae family. It has been reported to have analgesic, antispastic, sedative, anti-inflammatory, and other pharmacologic activities. Despite its critical pharmacological function, its metabolite profiling is still unclear. In this study, the in vivo metabolite profiling of skimmianine in rats was investigated using ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (UPLC/Q-TOF-MS). The metabolites were predicted using MetabolitePilot TM software. These predicted metabolites were further analyzed by MS² spectra, and compared with the detailed fragmentation pathway of the skimmianine standard and literature data. A total of 16 metabolites were identified for the first time in rat plasma, urine, and feces samples after oral administration of skimmianine. Skimmianine underwent extensive Phase I and Phase II metabolism in rats. The Phase I biotransformations of skimmianine consist of epoxidation of olefin on its furan ring (M1) followed by the hydrolysis of the epoxide ring (M4), hydroxylation (M2, M3), O -demethylation (M5-M7), didemethylation (M14-M16). The Phase II biotransformations include glucuronide conjugation (M8-M10) and sulfate conjugation (M11-M13). The epoxidation of 2,3-olefinic bond followed by the hydrolysis of the epoxide ring and O -demethylation were the major metabolic pathways of skimmianine. The results provide key information for understanding the biotransformation processes of skimmianine and the related furoquinoline alkaloids.

  8. [Simultaneous determination of four alkaloids in Corydalis decumbens (Thunb.) Pers. by high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Shen, Yan; Han, Chao; Liu, Cuiping; Zhou, Yongfang; Xia, Biqi; Zhu, Zhenou; Liu, Aili

    2011-02-01

    A method for the analysis of 4 alkaloids in Corydalis decumbens (Thunb.) Pers. was developed by high performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-MS/MS). The sample was extracted in methanol by ultrasonic, filtered and diluted with methanol for further analysis. The analysis was performed on a C18 column (150 mm x 2.1 mm, 3.5 microm) using a gradient elution program with the mobile phase of 0.2% acetic acid solution and acetonitrile. The analyte was determined by an electrospray ionization tandem mass spectrometry in multiple reactions monitoring (MRM) mode. The qualitative and quantitative analyses were based on the retention times and characteristic ion pairs consisting of one parent ion and two fragment ions of the analyte. The limits of detection (LODs) for 4 alkaloids were in the range of 0.02 - 0.2 microg/L, and the limits of quantification (LOQs) were in the range of 0.07 - 0.66 microg/L. The average recoveries were in the range of 93.6% - 103.5% for 4 alkaloids with the relative standard deviations below 3.8%. This method is reliable, sensitive and reproducible, and it can be used for the quality control of Corydalis decumbens (Thunb.) Pers. sample.

  9. Determination of molindone enantiomers in human plasma by high-performance liquid chromatography-tandem mass spectrometry using macrocyclic antibiotic chiral stationary phases.

    PubMed

    Jiang, Hongliang; Li, Yinghe; Pelzer, Mary; Cannon, Michelle J; Randlett, Christopher; Junga, Heiko; Jiang, Xiangyu; Ji, Qin C

    2008-05-30

    A sensitive and selective bioanalytical assay was developed and validated for the determination of enantiomeric molindone in human plasma using high-performance liquid chromatography-tandem mass spectrometry along with supported liquid extraction procedures. The chiral separation was evaluated and optimized on macrocyclic antibiotic type chiral stationary phases (CSPs) based on teicoplanin aglycone (Chirobiotic TAG) in polar organic, polar ionic, and reversed-phase mode chromatography, respectively. Complete baseline separation was achieved on a Chirobiotic TAG column under isocratic condition in reversed-phase chromatography. The method validation was conducted using a Chirobiotic TAG column (100 mm x 2.1 mm) over the curve range 0.100-100 ng/ml for each molindone enantiomer using 0.0500 ml of plasma sample. The flow rate was 0.8 ml/min and the total run time was 9 min. Supported liquid extraction in a 96-well plate format was used for sample preparation. Parameters including recovery, matrix effect, linearity, sensitivity, specificity, carryover, precision, accuracy, dilution integrity, and stability were evaluated. The intra- and inter-day precision and accuracy of the quality control samples at low, medium, and high concentration levels were RSD

  10. Quantification of steroid hormones in human serum by liquid chromatography-high resolution tandem mass spectrometry.

    PubMed

    Matysik, Silke; Liebisch, Gerhard

    2017-12-01

    A limited specificity is inherent to immunoassays for steroid hormone analysis. To improve selectivity mass spectrometric analysis of steroid hormones by liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been introduced in the clinical laboratory over the past years usually with low mass resolution triple-quadrupole instruments or more recently by high resolution mass spectrometry (HR-MS). Here we introduce liquid chromatography-high resolution tandem mass spectrometry (LC-MS/HR-MS) to further increase selectivity of steroid hormone quantification. Application of HR-MS demonstrates an enhanced selectivity compared to low mass resolution. Separation of isobaric interferences reduces background noise and avoids overestimation. Samples were prepared by automated liquid-liquid extraction with MTBE. The LC-MS/HR-MS method using a quadrupole-Orbitrap analyzer includes eight steroid hormones i.e. androstenedione, corticosterone, cortisol, cortisone, 11-deoxycortisol, 17-hydroxyprogesterone, progesterone, and testosterone. It has a run-time of 5.3min and was validated according to the U.S. Food and Drug Administration (FDA) and the European Medicines Agency (EMA) guidelines. For most of the analytes coefficient of variation were 10% or lower and LOQs were determined significantly below 1ng/ml. Full product ion spectra including accurate masses substantiate compound identification by matching their masses and ratios with authentic standards. In summary, quantification of steroid hormones by LC-MS/HR-MS is applicable for clinical diagnostics and holds also promise for highly selective quantification of other small molecules. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Profiling the indole alkaloids in yohimbe bark with ultra-performance liquid chromatography coupled with ion mobility quadrupole time-of-flight mass spectrometry

    USDA-ARS?s Scientific Manuscript database

    An ultra-high performance liquid chromatography-ion mobility- quadrupole time-of-flight mass spectrometry (UHPLC-IM-QTOF-MS) method was developed for profiling the indole alkaloids in yohimbe bark. Many indole alkaloids with the yohimbine core structure, plus methylated, oxidized, and reduced speci...

  12. Micro-polarimeter for high performance liquid chromatography

    DOEpatents

    Yeung, Edward E.; Steenhoek, Larry E.; Woodruff, Steven D.; Kuo, Jeng-Chung

    1985-01-01

    A micro-polarimeter interfaced with a system for high performance liquid chromatography, for quantitatively analyzing micro and trace amounts of optically active organic molecules, particularly carbohydrates. A flow cell with a narrow bore is connected to a high performance liquid chromatography system. Thin, low birefringence cell windows cover opposite ends of the bore. A focused and polarized laser beam is directed along the longitudinal axis of the bore as an eluent containing the organic molecules is pumped through the cell. The beam is modulated by air gap Faraday rotators for phase sensitive detection to enhance the signal to noise ratio. An analyzer records the beams's direction of polarization after it passes through the cell. Calibration of the liquid chromatography system allows determination of the quantity of organic molecules present from a determination of the degree to which the polarized beam is rotated when it passes through the eluent.

  13. [Determination of five synthetic sweeteners in wines using high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Ji, Chao; Feng, Feng; Chen, Zhengxing; Sun, Li; Chu, Xiaogang

    2010-08-01

    A high performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-ESI MS/MS) method for the determination of five synthetic sweeteners (acesulfame, sodium saccharin, sodium cyclamate, aspartame and neotame) in wines has been developed. The HPLC separation was carried out on an Ultimate C18 column (100 mm x 2.1 mm, 3 microm). Several parameters, including the composition and pH of the mobile phase, column temperature and the monitor ions, were optimized for improving the chromatographic performance and the sensitivity of determination. The results demonstrated that the separation can be completed in less than 5 min by gradient elution with 20 mmol/L ammonium formate and 0.1% (v/v) formic acid (pH 3.8) and methanol as the mobile phase. The column temperature was kept at 45 degrees C. When the analytes were detected by ESI -MS/MS under multiple reaction monitoring mode, the detection limits were 0.6, 5, 1, 0.8 and 0.2 microg/L for acesulfame, sodium saccharin, sodium cyclamate, aspartame and neotame, respectively. The average recoveries ranged from 87.2% to 103%. The relative standard deviations were not more than 1.2%. This method is rapid, accurate, highly sensitive and suitable for the quality control of low concentration of the synthetic sweeteners, which are illegally added to wines and other foods with complex matrices.

  14. Determination of ochratoxin A and T-2 toxin in alcoholic beverages by hollow fiber liquid phase microextraction and ultra high-pressure liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Romero-González, R; Frenich, A Garrido; Vidal, J L Martínez; Aguilera-Luiz, M M

    2010-06-30

    A new method for the determination of ochratoxin A and T-2 toxin in alcoholic beverages (wine and beer) by hollow fiber liquid microextraction was optimized. The extraction step was followed by ultra high-pressure liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The extraction procedure was based on the extraction of mycotoxins from the sample to the organic solvent (1-octanol) immobilized in the fiber, and afterwards, they were desorbed in a mixture of acetonitrile/water (80:20, v/v) at pH 7 prior to chromatographic determination. Different variables affecting the extraction process such as organic solvent, salt content, extraction time and desorption solution were studied. The developed method was validated in wine and beer, using white wine and alcoholic beer as representative matrices for both types of samples. Relative recoveries higher than 70% were obtained for the selected mycotoxins. Good linearity (R(2)>0.993) was obtained and quantification limits (0.02-0.09 microg L(-1)) below European regulatory levels were achieved. Repeatability, expressed as relative standard deviation, was always lower than 12%, whereas interday precision was lower than 21%. The proposed method was applied to the analysis of several types of wines and beers and ochratoxin A was detected in a rosé wine at 1.1 microg L(-1). Copyright 2010 Elsevier B.V. All rights reserved.

  15. Metabolic profiles of physalin A in rats using ultra-high performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    Feng, Xinchi; Liu, Hongxia; Chai, Liwei; Ding, Liqin; Pan, Guixiang; Qiu, Feng

    2017-03-01

    Physalin A, one of the major active components isolated from the calyces of Physalis alkekengi var. franchetii is considered to be a promising natural product due to its anti-inflammatory and excellent antitumor activities. Until now, only one paper is available from our group concerning identification of two sulfonate metabolites from rat feces after physalin A treatment. All the other researches related to physalin A were focused on its extraction, separation and biological activities. In this research, a rapid and reliable ultra-high-performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UPLC/Q-TOF-MS/MS) method was developed and employed for the comprehensive study of the metabolism of physalin A in vivo for the first time. A total of 24 proposed metabolites were identified in plasma, bile, urine and feces of rats after oral administration of physalin A. The results indicated that sulfonation, reduction and hydroxylation were the major metabolic pathways of physalin A in vivo. Furthermore, this research provides scientific and reliable support for full understanding of the metabolism of physalin A and the results could help to elucidate the safety and efficacy of physalin A, as well as other physalins. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Determination of fluoroquinolones in cattle manure-based biogas residue by ultrasonic-enhanced microwave-assisted extraction followed by online solid phase extraction-ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Lu, Xue-Feng; Zhou, Yang; Zhang, Jian; Ren, Yu-Peng

    2018-06-01

    The present work describes the development and application of an ultrasonic-enhanced microwave-assisted extraction (UEMAE) followed by online solid phase extraction (SPE)-ultra-high performance liquid chromatography-tandem mass spectrometry method for the analysis of 14 fluoroquinolones in cattle manure-based biogas residue (CMBBR). The UEMAE was performed using the mixed solution of sodium dihydrogen phosphate and disodium ethylenediamine tetraacetic acid, avoiding use of any organic solvent. The online SPE system employed two solid phase extraction columns in a parallel manner, and the extraction was performed by passing 1 mL of the extract through the column. Quantification was performed using standard spiked samples and structural analogue internal standard, which were indispensable to reduce the matrix effects. Validation parameters were performed and good linearity (R 2  > 0.99 in all cases) and precision (inter- and intra-day relative standard deviations were lower than 12.8%) were obtained. Limits of detection were as low as 0.021 ng ∙ g -1 and lower limits of quantification were 0.5 ng ∙ g -1 for all fluoroquinolones. The overall extraction recovery, which was the product of the UEMAE recovery and the online SPE recovery, was assessed for three concentration levels (0.8, 40 and 400 ng ∙ g -1 ) and acceptable values (74.3-99.3%) were found. As a part of the method validation, the developed method has been used to analyze real CMBBR samples. Nine fluoroquinolones were found in the concentration range of 0.9-74.6 ng ∙ g -1 , while five were not detected in the samples. The results showed the method could be adapted for screening the presence or the final fate of fluoroquinolones during fermentation of animal waste. Copyright © 2018. Published by Elsevier B.V.

  17. Ultra-trace levels analysis of microcystins and nodularin in surface water by on-line solid-phase extraction with high-performance liquid chromatography tandem mass spectrometry.

    PubMed

    Balest, Lydia; Murgolo, Sapia; Sciancalepore, Lucia; Montemurro, Patrizia; Abis, Pier Paolo; Pastore, Carlo; Mascolo, Giuseppe

    2016-06-01

    An on-line solid phase extraction coupled with high-performance liquid chromatography in tandem with mass spectrometry (on-line SPE/HPLC/MS-MS) method for the determination of five microcystins and nodularin in surface waters at submicrogram per liter concentrations has been optimized. Maximum recoveries were achieved by carefully optimizing the extraction sample volume, loading solvent, wash solvent, and pH of the sample. The developed method was also validated according to both UNI EN ISO IEC 17025 and UNICHIM guidelines. Specifically, ten analytical runs were performed at three different concentration levels using a reference mix solution containing the six analytes. The method was applied for monitoring the concentrations of microcystins and nodularin in real surface water during a sampling campaign of 9 months in which the ELISA method was used as standard official method. The results of the two methods were compared showing good agreement when the highest concentration values of MCs were found. Graphical abstract An on-line SPE/HPLC/MS-MS method for the determination of five microcystins and nodularin in surface waters at sub μg L(-1) was optimized and compared with ELISA assay method for real samples.

  18. Ultra-high-performance liquid chromatography tandem mass spectrometry determination of GHB, GHB-glucuronide in plasma and cerebrospinal fluid of narcoleptic patients under sodium oxybate treatment.

    PubMed

    Tittarelli, Roberta; Pichini, Simona; Pedersen, Daniel S; Pacifici, Roberta; Moresco, Monica; Pizza, Fabio; Busardò, Francesco Paolo; Plazzi, Giuseppe

    2017-05-01

    Sodium oxybate (Xyrem ® ), the sodium salt of γ- hydroxybutyric acid (GHB), is a first-line treatment of the symptoms induced by type 1 narcolepsy (NT1) and it is highly effective in improving sleep architecture, decreasing excessive daytime sleepiness and the frequency of cataplexy attacks. Using an ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) validated method, GHB was determined together with its glucuronide (GHB-gluc), in plasma and cerebrospinal fluid (CSF) samples of NT1 patients under sodium oxybate treatment. To characterize the plasma pharmacokinetics of GHB, three subjects with NT1 were administered at time 0 and 4h with 1.25, 1.5 and 3.55g Xyrem ® , respectively and had their blood samples collected at 7 time points throughout an 8-h session. CSF specimens, collected for orexin A measurement from the same three subjects 6h after their second administration, were also tested. The results obtained suggested that GHB plasma values increased disproportionally with the rising doses, (C max0-4 : 12.53, 32.95 and 69.62μg/mL; C max4-8 : 44.93, 75.03 and 111.93μg/mL for total Xyrem ® dose of 2.5, 3 and 7g respectively) indicating non-linear dose-response. GHB-Gluc was present only in traces in all plasma samples from treated patients, not changing with increasing Xyrem ® doses. GHB values of 5.62, 6.10 and 17.74μg/mL for 2, 3 and 7g Xyrem ® were found in CSF with a significant difference from control values. GHB-Gluc was found in negligible concentrations with no differences to those of control individuals. In conclusion this simple and fast UHPLC-MS/MS method proved useful for pharmacokinetic studies and therapeutic drug monitoring of GHB in narcoleptic patients treated with sodium oxybate. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Simultaneous detection of six urinary pteridines and creatinine by high-performance liquid chromatography-tandem mass spectrometry for clinical breast cancer detection.

    PubMed

    Burton, Casey; Shi, Honglan; Ma, Yinfa

    2013-11-19

    Recent preliminary studies have implicated urinary pteridines as candidate biomarkers in a growing number of malignancies including breast cancer. While the developments of capillary electrophoresis-laser induced fluorescence (CE-LIF), high performance liquid chromatography (HPLC), and liquid chromatography-mass spectroscopy (LC-MS) pteridine urinalyses among others have helped to enable these findings, limitations including poor pteridine specificity, asynchronous or nonexistent renal dilution normalization, and a lack of information regarding adduct formation in mass spectrometry techniques utilizing electrospray ionization (ESI) have prevented application of these techniques to a larger clinical setting. In this study, a simple, rapid, specific, and sensitive high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method has been developed and optimized for simultaneous detection of six pteridines previously implicated in breast cancer and creatinine as a renal dilution factor in urine. In addition, this study reports cationic adduct formation of urinary pteridines under ESI-positive ionization for the first time. This newly developed technique separates and detects the following six urinary pteridines: 6-biopterin, 6-hydroxymethylpterin, d-neopterin, pterin, isoxanthopterin, and xanthopterin, as well as creatinine. The method detection limit for the pteridines is between 0.025 and 0.5 μg/L, and for creatinine, it is 0.15 μg/L. The method was also validated by spiked recoveries (81-105%), reproducibility (RSD: 1-6%), and application to 25 real urine samples from breast cancer positive and negative samples through a double-blind study. The proposed technique was finally compared directly with a previously reported CE-LIF technique, concluding that additional or alternative renal dilution factors are needed for proper investigation of urinary pteridines as breast cancer biomarkers.

  20. Quantification of Fatty Acid Oxidation Products Using On-line High Performance Liquid Chromatography Tandem Mass Spectrometry

    PubMed Central

    Levison, Bruce S.; Zhang, Renliang; Wang, Zeneng; Fu, Xiaoming; DiDonato, Joseph A.; Hazen, Stanley L.

    2013-01-01

    Oxidized fatty acids formed via lipid peroxidation are implicated in pathological processes such as inflammation and atherosclerosis. A number of methods may be used to detect specific oxidized fatty acids containing a single or multiple combinations of epoxide, hydroxyl, ketone and hydroperoxide moieties on varying carbon chain lengths from C8 up to C30. Some of these methods are nonspecific and their use in biological systems is fraught with difficulty. Measures of specific-oxidized fatty acid derivatives help in identifying oxidation pathways in pathological processes. We used liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC-MS/MS) as efficient, selective and sensitive methods for identifying and analyzing multiple specific fatty acid peroxidation products in human plasma and other biological matrices. We then distilled the essential components of a number of these analyses to provide an efficient protocol by which fatty acid oxidation products and their parent compounds can be determined. In this protocol, addition of synthetic internal standard to the sample, followed by base hydrolysis at elevated temperature, and liquid-liquid phase sample extraction with lighter than water solvents facilitates isolation of the oxidized fatty acid species. These species can be identified and accurately quantified using stable isotope dilution and multiple reaction monitoring. Use of a coupled multiplexed gradient HPLC system on the front end enables high-throughput chromatography and more efficient use of mass spectrometer time. PMID:23499838

  1. Detailed phenolic composition of Vidal grape pomace by ultrahigh-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Luo, Lanxin; Cui, Yan; Zhang, Shuting; Li, Lingxi; Suo, Hao; Sun, Baoshan

    2017-11-15

    Vidal Blanc grape (Vitis vinifera cv.) is the predominant white grape variety used for the production of icewine in China's Liaoning province. In this paper, the development and validation of the method by ultrahigh-performance liquid chromatography-tandem mass spectrometry has been performed for determination of the detailed phenolic composition in the skin, seed and stem of Vidal grapes. The validation of the method was realized by calculating the linearity, repeatability, precision, stability and the limits of detection (LOD) and quantification (LOQ) of standard solutions. All the curves exhibited good linearity (r 2 >0.9997) and the LOD and LOQ were in the range of 0.002-0.025 and 0.006-0.086μg/ml, respectively. Good repeatability (RSD<4.3%) and stability (RSD<3.7%) were also found. Results confirmed that the developed method was more effective and sensitive for simultaneous determination of the major phenolic compounds in Vidal grape pomace. The optimized and validated method of ultrahigh-performance liquid chromatography tandem two complementary techniques, fourier transform ion cyclotron resonance mass spectrometry and triple-quadrupole mass spectrometry, allowed to identify and quantify up to 35 phenolic compounds in Vidal grape pomace, which has, as far as we know, been reported this grapevine variety for the first time. Seeds, skins and stems exhibited different qualitative and quantitative phenolic profiles. These results provided useful information for recovery of phenolic antioxidants from different parts of icewine pomace. Copyright © 2017. Published by Elsevier B.V.

  2. A rapid method for the simultaneous determination of L-ascorbic acid and acetylsalicylic acid in aspirin C effervescent tablet by ultra performance liquid chromatography-tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    Wabaidur, Saikh Mohammad; Alothman, Zeid Abdullah; Khan, Mohammad Rizwan

    2013-05-01

    In present study, a rapid and sensitive method using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed for the simultaneous determination of L-ascorbic acid and acetylsalicylic acid in aspirin C effervescent tablet. The optimum chromatographic separation was carried out on a reversed phase Waters® Acquity UPLC BEH C18 column (1.7 μm particle size, 100 mm × 2.1 mm ID) with an isocratic elution profile and mobile phase consisting of 0.1% formic acid in water and acetonitrile (75:25, v/v, pH 3.5) at flow rate of 0.5 mL min-1. The influences of mobile phase composition, flow rate and pH on chromatographic resolution were investigated. The total chromatographic analysis time was as short as 2 min with excellent resolution. Detection and quantification of the target compounds were carried out with a triple quadrupole mass spectrometer using negative electrospray ionization (ESI) and multiple reaction monitoring (MRM) modes. The performance of the method was evaluated and very low limits of detection less than 0.09 μg g-1, excellent coefficient correlation (r2 > 0.999) with liner range over a concentration range of 0.1-1.0 μg g-1 for both L-ascorbic acid and acetylsalicylic acid, and good intraday and interday precisions (relative standard deviations (R.S.D.) <3%), were obtained. Comparison of system performance with traditional liquid chromatography-photo diode array detector (HPLC-PDA) was made with respect to analysis time, sensitivity, linearity and precisions. The proposed UPLC-MS/MS method was found to be reproducible and appropriate for quantitative analysis of L-ascorbic acid and acetylsalicylic acid in aspirin C effervescent tablet.

  3. High Performance Liquid Chromatography

    NASA Astrophysics Data System (ADS)

    Talcott, Stephen

    High performance liquid chromatography (HPLC) has many applications in food chemistry. Food components that have been analyzed with HPLC include organic acids, vitamins, amino acids, sugars, nitrosamines, certain pesticides, metabolites, fatty acids, aflatoxins, pigments, and certain food additives. Unlike gas chromatography, it is not necessary for the compound being analyzed to be volatile. It is necessary, however, for the compounds to have some solubility in the mobile phase. It is important that the solubilized samples for injection be free from all particulate matter, so centrifugation and filtration are common procedures. Also, solid-phase extraction is used commonly in sample preparation to remove interfering compounds from the sample matrix prior to HPLC analysis.

  4. Comparative analysis of main bio-active components in the herb pair Danshen-Honghua and its single herbs by ultra-high performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry.

    PubMed

    Qu, Cheng; Pu, Zong-Jin; Zhou, Gui-Sheng; Wang, Jun; Zhu, Zhen-Hua; Yue, Shi-Jun; Li, Jian-Ping; Shang, Li-Li; Tang, Yu-Ping; Shi, Xu-Qin; Liu, Pei; Guo, Jian-Ming; Sun, Jing; Tang, Zhi-Shu; Zhao, Jing; Zhao, Bu-Chang; Duan, Jin-Ao

    2017-09-01

    A sensitive, reliable, and powerful ultra-high performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry method was developed for simultaneous quantification of the 15 main bio-active components including phenolic acids and flavonoids within 13 min for the first time. The proposed method was first reported and validated by good linearity (r 2  > 0.9975), limit of detection (1.12-7.01 ng/mL), limit of quantification (3.73-23.37 ng/mL), intra- and inter-day precisions (RSD ≤ 1.92%, RSD ≤ 2.45%), stability (RSD ≤ 5.63%), repeatability (RSD ≤ 4.34%), recovery (96.84-102.12%), and matrix effects (0.92-1.02). The established analytical methodology was successfully applied to comparative analysis of main bio-active components in the herb pair Danshen-Honghua and its single herbs. Compared to the single herb, the content of most flavonoid glycosides was remarkably increased in their herb pair, and main phenolic acids were decreased, conversely. The content changes of the main components in the herb pair supported the synergistic effects on promoting blood circulation and removing blood stasis. The results provide a scientific basis and reference for the quality control of Danshen-Honghua herb pair and the drug interactions based on variation of bio-active components in herb pairs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Pre-analytical and analytical variation of drug determination in segmented hair using ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Nielsen, Marie Katrine Klose; Johansen, Sys Stybe; Linnet, Kristian

    2014-01-01

    Assessment of total uncertainty of analytical methods for the measurements of drugs in human hair has mainly been derived from the analytical variation. However, in hair analysis several other sources of uncertainty will contribute to the total uncertainty. Particularly, in segmental hair analysis pre-analytical variations associated with the sampling and segmentation may be significant factors in the assessment of the total uncertainty budget. The aim of this study was to develop and validate a method for the analysis of 31 common drugs in hair using ultra-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) with focus on the assessment of both the analytical and pre-analytical sampling variations. The validated method was specific, accurate (80-120%), and precise (CV≤20%) across a wide linear concentration range from 0.025-25 ng/mg for most compounds. The analytical variation was estimated to be less than 15% for almost all compounds. The method was successfully applied to 25 segmented hair specimens from deceased drug addicts showing a broad pattern of poly-drug use. The pre-analytical sampling variation was estimated from the genuine duplicate measurements of two bundles of hair collected from each subject after subtraction of the analytical component. For the most frequently detected analytes, the pre-analytical variation was estimated to be 26-69%. Thus, the pre-analytical variation was 3-7 folds larger than the analytical variation (7-13%) and hence the dominant component in the total variation (29-70%). The present study demonstrated the importance of including the pre-analytical variation in the assessment of the total uncertainty budget and in the setting of the 95%-uncertainty interval (±2CVT). Excluding the pre-analytical sampling variation could significantly affect the interpretation of results from segmental hair analysis. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  6. Fast analysis of doping agents in urine by ultra-high-pressure liquid chromatography-quadrupole time-of-flight mass spectrometry. II: Confirmatory analysis.

    PubMed

    Badoud, F; Grata, E; Perrenoud, L; Saugy, M; Rudaz, S; Veuthey, J-L

    2010-06-18

    For doping control, analyses of samples are generally achieved in two steps: a rapid screening and, in the case of a positive result, a confirmatory analysis. A two-step methodology based on ultra-high-pressure liquid chromatography coupled to a quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS) was developed to screen and confirm 103 doping agents from various classes (e.g., beta-blockers, stimulants, diuretics, and narcotics). The screening method was presented in a previous article as part I (i.e., Fast analysis of doping agents in urine by ultra-high-pressure liquid chromatography-quadrupole time-of-flight mass spectrometry. Part I: screening analysis). For the confirmatory method, basic, neutral and acidic compounds were extracted by a dedicated solid-phase extraction (SPE) in a 96-well plate format and detected by MS in the tandem mode to obtain precursor and characteristic product ions. The mass accuracy and the elemental composition of precursor and product ions were used for compound identification. After validation including matrix effect determination, the method was considered reliable to confirm suspect results without ambiguity according to the positivity criteria established by the World Anti-Doping Agency (WADA). Moreover, an isocratic method was developed to separate ephedrine from its isomer pseudoephedrine and cathine from phenylpropanolamine in a single run, what allowed their direct quantification in urine. Copyright (c) 2010 Elsevier B.V. All rights reserved.

  7. Optimization of ultra-performance liquid chromatography (UPLC) with fluorescence detector (FLD) method for the quantitative determination of selected neurotransmitters in rat brain.

    PubMed

    Stragierowicz, Joanna; Daragó, Adam; Brzeźnicki, Sławomir; Kilanowicz, Anna

    2017-07-26

    Glutamate (Glu) and γ-aminobutyric acid (GABA) are the main neurotransmitters in the central nervous system for excitatory and inhibitory processes, respectively. Monitoring these neurotransmitters is an essential tool in establishing pathological functions, among others in terms of occupational exposure to toxic substances. We present modification of the HPLC (high-performance liquid chromatography) to the UPLC (ultra-performance liquid chromatography) method for the simultaneous determination of glutamate and γ-aminobutyric acid in a single injection. The isocratic separation of these neurotransmitter derivatives was performed on Waters Acquity BEH (ethylene bridged hybrid) C18 column with particle size of 1.7 μm at 35°C using a mobile phase consisting of 0.1 M acetate buffer (pH 6.0) and methanol (60:40, v/v) at a flow rate of 0.3 ml/min. The analytes were detected with the fluorescence detector (FLD) using derivatization with o-phthaldialdehyde (OPA), resulting in excitation at 340 nm and emission at 455 nm. Several validation parameters including linearity (0.999), accuracy (101.1%), intra-day precision (1.52-1.84%), inter-day precision (2.47-3.12%), limit of detection (5-30 ng/ml) and quantification (100 ng/ml) were examined. The developed method was also used for the determination of these neurotransmitters in homogenates of selected rat brain structures. The presented UPLC-FLD is characterized by shorter separation time (3.5 min), which is an adaptation of the similar HPLC methods and is an alternative for more expensive references techniques such as liquid chromatography coupled with tandem mass-spectrometry (LC-MS/MS) methods. Med Pr 2017;68(5):583-591. This work is available in Open Access model and licensed under a CC BY-NC 3.0 PL license.

  8. [Simultaneous determination of 16 flavonoids in the ginkgo dietary supplement tea by high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Jiang, Yalan; Huang, Fang; Wu, Fuhai; Wu, Huiqin; Huang, Xiaolan; Deng, Xin

    2015-10-01

    A method for the determination of 16 functional components of ginkgo dietary supplement tea such as catechin, vitexin, puerarin, isoflavoues aglycone, silymarin, quercetin, luteolin, apigenin, naringenin, hesperitin dihydrochalcone, kaempferol, hesperitin, isorhamnetin, baicalein, nobiletin and tangeretin by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was proposed. The conditions of chromatography and mass spectrometry were optimized. The 16 flavonoids were separated on a C18 chromatographic column with acetonitrile and water (additional 0.1% formic acid) as mobile phases under gradient elution at a flow rate of 0.25 mL/min. The determination was conducted by tandem mass spectrometry in positive ESI mode under multiple reaction monitoring (MRM) mode. Good linearities for all the compounds, with correlation coefficients over 0.996, were acquired. The recoveries were in the range of 70.9% to 100.0% (n = 6), while the relative standard deviations (RSDs) were less than 10%. The results showed that the nine flavonoids, which were kaempferol, quercetin, hesperitin, vitexin, luteolin, catechin, apigenin, naringenin and isorhamnetin, were higher in contents among the 16 flavonoids in real samples, and they constituted up to 99.6% of the total flavonoids. The contents of these nine flavonoids can be considered as the quality control index of the ginkgo dietary supplement tea. The method proved to be rapid, selective, sensitive and stable, and it can be applied to control the quality of the ginkgo dietary supplement tea.

  9. Method transfer from high-pressure liquid chromatography to ultra-high-pressure liquid chromatography. II. Temperature and pressure effects.

    PubMed

    Åsberg, Dennis; Samuelsson, Jörgen; Leśko, Marek; Cavazzini, Alberto; Kaczmarski, Krzysztof; Fornstedt, Torgny

    2015-07-03

    The importance of the generated temperature and pressure gradients in ultra-high-pressure liquid chromatography (UHPLC) are investigated and compared to high-pressure liquid chromatography (HPLC). The drug Omeprazole, together with three other model compounds (with different chemical characteristics, namely uncharged, positively and negatively charged) were used. Calculations of the complete temperature profile in the column at UHPLC conditions showed, in our experiments, a temperature difference between the inlet and outlet of 16 °C and a difference of 2 °C between the column center and the wall. Through van't Hoff plots, this information was used to single out the decrease in retention factor (k) solely due to the temperature gradient. The uncharged solute was least affected by temperature with a decrease in k of about 5% while for charged solutes the effect was more pronounced, with k decreases up to 14%. A pressure increase of 500 bar gave roughly 5% increase in k for the uncharged solute, while omeprazole and the other two charged solutes gave about 25, 20 and 15% increases in k, respectively. The stochastic model of chromatography was applied to estimate the dependence of the average number of adsorption/desorption events (n) and the average time spent by a molecule in the stationary phase (τs) on temperature and pressure on peak shape for the tailing, basic solute. Increasing the temperature yielded an increase in n and decrease in τs which resulted in less skew at high temperatures. With increasing pressure, the stochastic modeling gave interesting results for the basic solute showing that the skew of the peak increased with pressure. The conclusion is that pressure effects are more pronounced for both retention and peak shape than the temperature effects for the polar or charged compounds in our study. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Optimization and application of fabric phase sorptive extraction coupled to ultra-high performance liquid chromatography tandem mass spectrometry for the determination of cytostatic drug residues in environmental waters.

    PubMed

    Santana-Viera, Sergio; Guedes-Alonso, Rayco; Sosa-Ferrera, Zoraida; Santana-Rodríguez, José Juan; Kabir, Abuzar; Furton, Kenneth G

    2017-12-22

    Every year, hundreds of tons of organic pollutants reach the environment through effluents released from wastewater treatment plants worldwide, and many of these compounds have harmful effects on the aquatic ecosystem. A new class of emerging pollutants of high concern is cytostatic drugs, which are designed to treat different types of cancers by attacking cells. Environmental concentrations of cytostatic drugs are known to be in the range of ngL -1 , and for this reason, it is imperative to develop analytical methods of extraction and preconcentration to allow for subsequent instrumental analysis of these drugs. In this work, a rapid, simple and green method for the analysis of seven cytostatic drug compounds that are commonly used in anti-cancer therapies was developed using a novel extraction process based on a powerful miniaturized technique, fabric phase sorptive extraction (FPSE) coupled to ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). The major parameters that affect the extraction process were optimized. The new method shows good linearity, with a relative standard deviation (RSD) of less than 12%. Relative recoveries higher than 40% were obtained for the studied compounds, and the detection limit of the method was within the values at which these compounds are usually found in environmental water (0.20ngL -1 to 80ngL -1 ). The Limit of Quantification ranged from 0.68 to 267ngL -1 . Significant suppression of the signal due to the matrix effect, a common shortcoming attributed to interference from the extraction process as well as the use of ionization mode, was not observed. Subsequently, the method was applied to real wastewater samples from an effluent obtained from a hospital area and three wastewater treatment plants located in Gran Canaria Island, Spain. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Determination of bisphenol AF (BPAF) in tissues, serum, urine and feces of orally dosed rats by ultra-high-pressure liquid chromatography-electrospray tandem mass spectrometry.

    PubMed

    Yang, Yunjia; Yin, Jie; Yang, Yi; Zhou, Naiyuan; Zhang, Jing; Shao, Bing; Wu, Yongning

    2012-07-15

    As a homologue of bisphenol A (BPA), there is concern about the potential reproductive and developmental toxicity of bisphenol AF (BPAF) based on in vitro tests. In this study, a simple and universal analytical method was developed for the determination of trace BPAF in various tissues and excreta of rats after they were orally dosed. The samples were hydrolyzed with glucuronidase/arylsulfatase followed by ultrasonic extraction with acetonitrile. The crude extract was purified with a mixed-mode anion exchange (Oasis MAX) solid-phase extraction (SPE) cartridge. Separation and quantification was then conducted by ultra-high-pressure liquid chromatography/electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) in negative ionization mode. The recoveries at three fortification levels in different biological samples were from 71.0% to 102.3% with relative standard deviations no more than 13.2% (n=6). The quantification limits of the method were from 0.5 μg/kg to 3 μg/kg depending on the matrix. This method was successfully applied to the determination of BPAF in tissues, serum, urine and feces of orally dosed rats. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. Vitamin B12 determination in milk, whey and different by-products of ricotta cheese production by ultra performance liquid chromatography coupled with tandem mass spectrometry

    PubMed Central

    Repossi, Adele; Zironi, Elisa; Gazzotti, Teresa; Serraino, Andrea; Pagliuca, Giampiero

    2017-01-01

    Vitamin B12 (cobalamin) is a metal complex composed of a central cobalt ion bonded to six ligands. It is essential for major biological functions such as protein, fat and carbohydrate metabolism, the maintenance of the central nervous system, and the formation of red blood cells. Since mammals cannot synthesize cobalamin, dietary intake represents the only natural source for humans. Dairy products can provide significant levels of cobalamin; moreover, the European Food Safety Authority (EFSA) panel has set the recommended intake at 4 μg/day for adults. Vitamin B12 content was determined in milk and several matrices related to the process of transformation of the residual whey from Parmigiano Reggiano cheese-making to obtain ricotta cheese. In addition, vitamin B12 degradation during ricotta cheese shelf-life was studied. The analyses were performed using an ultra performance liquid chromatography-tandem mass spectrometry method. Results show that vitamin B12 amount in ricotta from dairy and experimental cheese-making brings respectively 1/8 to 1/4 of the adequate intake in adults established by EFSA. In addition, shelf-life experiment shows that cobalamine is fairly rapidly degraded in ricotta: light effect seems to be significant, even if the light exposure is short. The use of photoprotective packaging material increases B12 shelf-life in the early stage of storage. PMID:29564230

  13. [Determination of 23 antibiotics and 3 β-agonists in livestock drinking water by ultra performance liquid chromatography-tandem mass spectrometry coupled with solid-phase extraction].

    PubMed

    Shi, Ao

    2016-02-01

    A method has been developed for the simultaneous determination of 23 antibiotics (four categories) and 3 β-agonists in livestock drinking water using solid-phase extraction and ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (UPLC-ESI MS/MS). The samples were adjusted pH to 5. 0, added Na2EDTA, enriched and cleaned-up by an HLB solid-phase extraction cartridge. The target compounds were confirmed and quantified by UPLC-ESI MS/MS with external standard method for the anti- biotics and internal standard method for the β-agonists. The recoveries were assessed by using lab tap water as matrix. The average recoveries of the 23 antibiotics and the 3 β-agonists were in the range of 50. 7%-104. 6% and the relative standard deviations (RSDs) were 2. 6%-8. 8% (n= 3). Under the optimal conditions, the calibration curves of the 23 antibiotics and the 3 β-agonists showed good linearity with the correlation coefficients better than 0. 994. The limits of detection (LODs, S/N≥3) ranged from 0. 01-0. 20 ng/L. The developed method was applied to analyze the livestock drinking waters in 36 Beijing intensive livestock farms. The results showed that some antibiotics were detected.

  14. High-Performance Liquid Chromatography-Mass Spectrometry.

    ERIC Educational Resources Information Center

    Vestal, Marvin L.

    1984-01-01

    Reviews techniques for online coupling of high-performance liquid chromatography with mass spectrometry, emphasizing those suitable for application to nonvolatile samples. Also summarizes the present status, strengths, and weaknesses of various techniques and discusses potential applications of recently developed techniques for combined liquid…

  15. Characterization of the multiple components of Acanthopanax Senticosus stem by ultra high performance liquid chromatography with quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    Sun, Hui; Liu, Jianhua; Zhang, Aihua; Zhang, Ying; Meng, Xiangcai; Han, Ying; Zhang, Yingzhi; Wang, Xijun

    2016-02-01

    Acanthopanax Senticosus Harms. has been used widely in traditional Chinese medicine for the treatment of chronic bronchitis, neurasthenia, hypertension and ischemic heart disease. However, the in vivo constituents of the stem of Acanthopanax Senticosus remain unknown. In this paper, ultra high performance liquid chromatography with electrospray ionization quadrupole time-of-flight mass spectrometry and the MarkerLynx(TM) software combined with multiple data processing approach were used to study the constituents in vitro and in vivo. The aqueous extract from the Acanthopanax Senticosus stem and the compositions in rat serum after intragastric administration were completely analyzed. Consequently, 115 compounds in the aqueous extract from Acanthopanax Senticosus stem and 41 compounds absorbed into blood were characterized. Of the 115 compounds in vitro, 54 were reported for first time, including sinapyl alcohol, sinapyl alcohol diglucoside, and 1-O-sinapoyl-β-D-glucose. In the 41 compounds in vivo, 7 were prototype components and 34 were metabolites which were from 21 components of aqueous extract from Acanthopanax Senticosus stem, and the metabolic pathways of the metabolites were elucidated for first time. The results narrowed the range of screening the active components and provided a basis for the study of action mechanism and pharmacology. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Quantification of vitamin B6 vitamers in human cerebrospinal fluid by ultra performance liquid chromatography-tandem mass spectrometry.

    PubMed

    van der Ham, M; Albersen, M; de Koning, T J; Visser, G; Middendorp, A; Bosma, M; Verhoeven-Duif, N M; de Sain-van der Velden, M G M

    2012-01-27

    Since vitamin B6 is essential for normal functioning of the central nervous system, there is growing need for sensitive analysis of B6 vitamers in cerebrospinal fluid (CSF). This manuscript describes the development and validation of a rapid, sensitive and accurate method for quantification of the vitamin B6 vitamers pyridoxal (PL), pyridoxamine (PM), pyridoxine (PN), pyridoxic acid (PA), pyridoxal 5'-phosphate (PLP), pyridoxamine 5'-phosphate (PMP) and pyridoxine 5'-phosphate (PNP) in human CSF. The method is based on ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with a simple sample preparation procedure of protein precipitation using 50 g L(-1) trichloroacetic acid containing stable isotope labeled internal standards: PL-D(3) for PL and PM, PN-(13)C(4) for PN, PA-D(2) for PA and PLP-D(3) for the phosphorylated vitamers. B6 vitamers were separated (Acquity HSS-T3 UPLC column) with a buffer containing acetic acid, heptafluorobutyric acid and acetonitrile. Positive electrospray ionization was used to monitor transitions m/z 168.1→150.1 (PL), 169.1→134.1 (PM), 170.1→134.1 (PN), 184.1→148.1 (PA), 248.1→150.1 (PLP), 249.1→232.1 (PMP) and 250.1→134.1 (PNP). The method was validated at three concentration levels for each B6 vitamer in CSF. Recoveries of the internal standards were between 93% and 96%. Intra- and inter-assay variations were below 20%. Accuracy tests showed deviations from 3% (PN) to 39% (PMP). Limits of quantification were in the range of 0.03-5.37 nM. Poor results were obtained for quantification of PNP. The method was applied to CSF samples of 20 subjects and two patients on pyridoxine supplementation. Using minimal CSF volumes this method is suitable for implementation in a routine diagnostic setting. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. Quantitative determination of hederagenin in rat plasma and cerebrospinal fluid by ultra fast liquid chromatography-tandem mass spectrometry method.

    PubMed

    Yang, Xuemei; Li, Guoliang; Chen, Lingyun; Zhang, Cong; Wan, Xinxiang; Xu, Jiangping

    2011-07-01

    A rapid, sensitive and selective method was developed for the quantitative determination of hederagenin in rat plasma and cerebrospinal fluid (CSF) by ultra fast liquid chromatography-tandem mass spectrometry (UFLC-MS/MS). It has been successfully applied in a pharmacokinetic study of hederagenin in the central nervous system (CNS). Sample pretreatment involved a simple protein precipitation with methanol and a one-step extraction with ethyl acetate. Separation was carried out in a Shim-pack XR-ODS II (75 mm × 2.0 mm, i.d., 2.1 μm) column with gradient elution at a flow rate of 0.35 mL/min. The mobile phase was 5mM ammonium acetate and acetonitrile. Detection was performed in a triple-quadruple tandem mass spectrometer by multiple-reaction-monitoring mode via electrospray ionization. A linear calibration curve for hederagenin was obtained over a concentration range of 0.406 (lower limit of quantification, LLOQ) to 203 ng/mL (r² > 0.99) for both plasma and CSF. The intra-day and inter-day precision (relative standard deviation, RSD) values were less than 15%. At all quality control (QC) levels, the accuracy (relative error, RE) was within -9.0% and 11.1% for plasma and CSF, respectively. The pharmacokinetics results indicated that hederagenin could pass through the blood-brain barrier. This UFLC-MS/MS method demonstrates higher sensitivity and sample throughput than previous methods. It was also successfully applied to the pharmacokinetic study of hederagenin following oral administration of Fructus akebiae extract in rats. Copyright © 2011 Elsevier B.V. All rights reserved.

  18. Collaborative trial validation study of two methods, one based on high performance liquid chromatography-tandem mass spectrometry and on gas chromatography-mass spectrometry for the determination of acrylamide in bakery and potato products.

    PubMed

    Wenzl, Thomas; Karasek, Lubomir; Rosen, Johan; Hellenaes, Karl-Erik; Crews, Colin; Castle, Laurence; Anklam, Elke

    2006-11-03

    A European inter-laboratory study was conducted to validate two analytical procedures for the determination of acrylamide in bakery ware (crispbreads, biscuits) and potato products (chips), within a concentration range from about 20 microg/kg to about 9000 microgg/kg. The methods are based on gas chromatography-mass spectrometry (GC-MS) of the derivatised analyte and on high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) of native acrylamide. Isotope dilution with isotopically labelled acrylamide was an integral part of both methods. The study was evaluated according to internationally accepted guidelines. The performance of the HPLC-MS/MS method was found to be superior to that of the GC-MS method and to be fit-for-the-purpose.

  19. Direct analysis of 18 flavonol glycosides, aglycones and terpene trilactones in Ginkgo biloba tablets by matrix solid phase dispersion coupled with ultra-high performance liquid chromatography tandem triple quadrupole mass spectrometry.

    PubMed

    Liu, Xin-Guang; Yang, Hua; Cheng, Xiao-Lan; Liu, Lei; Qin, Yong; Wang, Qi; Qi, Lian-Wen; Li, Ping

    2014-08-01

    Analysis and quality control of Ginkgo biloba have been comprehensively studied. However, little attention has been devoted to the simultaneous extraction and analysis of flavonols and terpene trilactones, especially for direct quantification of flavonol glycosides. This work described a rapid strategy for one-step extraction and quantification of the components. A matrix solid phase dispersion (MSPD) method was designed for the extraction of ginkgo ingredients and compared with the heat-reflux and ultrasonic extraction methods. An ultra-high performance liquid chromatography (UHPLC)-tandem-triple-quadrupole-mass spectrometry (QQQ-MS) method was developed for detection of the 18 components, including 10 original flavonol glycosides, 3 aglycones, and 5 lactones. Subsequently, the proposed strategy was used for the analysis of 12 G. biloba tablets. Results showed that MSPD produced comparable extraction efficiency but consumed less time and required lower solvent volumes compared with conventional methods. Without hydrolysis, the concentration detected was much closer to the original in the sample. The total flavonol glycoside contents in ginkgo tablets ranged from 3.59 to 125.21μgmg(-1), and the terpene trilactone varied from 3.45 to 57.8μgmg(-1) among different manufacturers. In conclusion, the proposed MSPD and UHPLC-QQQ-MS is rapid and sensitive in providing comprehensive profile of chemical constituents especially the genuine flavonol glycosides for improved quality control of ginkgo products. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. An ultra-high performance liquid chromatography method to determine the skin penetration of an octyl methoxycinnamate-loaded liquid crystalline system.

    PubMed

    Prado, A H; Borges, M C; Eloy, J O; Peccinini, R G; Chorilli, M

    2017-10-01

    Cutaneous penetration is a critical factor in the use of sunscreen, as the compounds should not reach systemic circulation in order to avoid the induction of toxicity. The evaluation of the skin penetration and permeation of the UVB filter octyl methoxycinnamate (OMC) is essential for the development of a successful sunscreen formulation. Liquid-crystalline systems are innovative and potential carriers of OMC, which possess several advantages, including controlled release and protection of the filter from degradation. In this study, a new and effective method was developed using ultra-high performance liquid chromatography (UPLC) with ultraviolet detection (UV) for the quantitative analysis of penetration of OMC-loaded liquid crystalline systems into the skin. The following parameters were assessed in the method: selectivity, linearity, precision, accuracy, robustness, limit of detection (LOD), and limit of quantification (LOQ). The analytical curve was linear in the range from 0.25 to 250 μg.m-1, precise, with a standard deviation of 0.05-1.24%, with an accuracy in the range from 96.72 to 105.52%, and robust, with adequate values for the LOD and LOQ of 0.1 and 0.25 μg.mL -1, respectively. The method was successfully used to determine the in vitro skin permeation of OMC-loaded liquid crystalline systems. The results of the in vitro tests on Franz cells showed low cutaneous permeation and high retention of the OMC, particularly in the stratum corneum, owing to its high lipophilicity, which is desirable for a sunscreen formulation.

  1. Simultaneous analysis of hydrochlorothiazide, triamterene and reserpine in rat plasma by high performance liquid chromatography and tandem solid-phase extraction.

    PubMed

    Li, Hang; He, Junting; Liu, Qin; Huo, Zhaohui; Liang, Si; Liang, Yong

    2011-03-01

    A tandem solid-phase extraction method (SPE) of connecting two different cartridges (C(18) and MCX) in series was developed as the extraction procedure in this article, which provided better extraction yields (>86%) for all analytes and more appropriate sample purification from endogenous interference materials compared with a single cartridge. Analyte separation was achieved on a C(18) reversed-phase column at the wavelength of 265 nm by high-performance liquid chromatography (HPLC). The method was validated in terms of extraction yield, precision and accuracy. These assays gave mean accuracy values higher than 89% with RSD values that were always less than 3.8%. The method has been successfully applied to plasma samples from rats after oral administration of target compounds. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Metabolite identification and pharmacokinetic profiling of PP242, an ATP-competitive inhibitor of mTOR using ultra high-performance liquid chromatography and mass spectrometry.

    PubMed

    Rashid, Md Mamunur; Lee, Hyunbeom; Jung, Byung Hwa

    2018-01-01

    PP242 is a second generation novel selective ATP-competitive inhibitor of mTOR that displayed promising anti-cancer activity over several cancer types by inhibiting both the complexes of mTOR (mTORC1 and mTORC2). The purpose of this study is to identify the possible metabolites and to evaluate the pharmacokinetic profile of PP242 after a single oral administration to Sprague-Dawley (SD) rats. Two metabolites, including one phase I and one phase II, were identified by in vitro and in vivo studies using rat liver microsomes (RLMs) as well as rat plasma, urine and feces, respectively, through ultra high-performance liquid chromatography-linear ion trap quadrupole-orbitrap-mass spectrometry (UHPLC-LTQ-Orbitrap-MS). The major biotransformation pathways of PP242 were hydroxylation and glucuronide conjugation. Additionally, a simple and rapid quantification method was developed and validated. The method recovery was within 79.7-84.6%, whereas the matrix effect was 78.1-96.0% in all three quality control (QC) concentrations (low, medium and high) including the LLOQ. Other parameters showed acceptable results according to the US food and drug administration (FDA) guidelines for bioanalytical method validation. Afterwards, pharmacokinetic parameters were evaluated in rat plasma by successfully applying the validated method using liquid chromatography-tandem mass spectrometry (LC-MS/MS). After a single oral administration at a dose of 5mg/kg, the maximum plasma concentration (C max ) of PP242 was 0.17±0.08μg/mL, while the elimination was moderately fast (T 1/2 : 172.18±45.54min). All of the obtained information on the metabolite identification and pharmacokinetic parameter elucidation could facilitate the further development of PP242. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Ultra-performance liquid chromatography/tandem mass spectrometric quantification of structurally diverse drug mixtures using an ESI-APCI multimode ionization source.

    PubMed

    Yu, Kate; Di, Li; Kerns, Edward; Li, Susan Q; Alden, Peter; Plumb, Robert S

    2007-01-01

    We report in this paper an ultra-performance liquid chromatography/tandem mass spectrometric (UPLC(R)/MS/MS) method utilizing an ESI-APCI multimode ionization source to quantify structurally diverse analytes. Eight commercial drugs were used as test compounds. Each LC injection was completed in 1 min using a UPLC system coupled with MS/MS multiple reaction monitoring (MRM) detection. Results from three separate sets of experiments are reported. In the first set of experiments, the eight test compounds were analyzed as a single mixture. The mass spectrometer was switching rapidly among four ionization modes (ESI+, ESI-, APCI-, and APCI+) during an LC run. Approximately 8-10 data points were collected across each LC peak. This was insufficient for a quantitative analysis. In the second set of experiments, four compounds were analyzed as a single mixture. The mass spectrometer was switching rapidly among four ionization modes during an LC run. Approximately 15 data points were obtained for each LC peak. Quantification results were obtained with a limit of detection (LOD) as low as 0.01 ng/mL. For the third set of experiments, the eight test compounds were analyzed as a batch. During each LC injection, a single compound was analyzed. The mass spectrometer was detecting at a particular ionization mode during each LC injection. More than 20 data points were obtained for each LC peak. Quantification results were also obtained. This single-compound analytical method was applied to a microsomal stability test. Compared with a typical HPLC method currently used for the microsomal stability test, the injection-to-injection cycle time was reduced to 1.5 min (UPLC method) from 3.5 min (HPLC method). The microsome stability results were comparable with those obtained by traditional HPLC/MS/MS.

  4. Identification of Ginkgo biloba supplements adulteration using high performance thin layer chromatography and ultra high performance liquid chromatography-diode array detector-quadrupole time of flight-mass spectrometry.

    PubMed

    Avula, Bharathi; Sagi, Satyanarayanaraju; Gafner, Stefan; Upton, Roy; Wang, Yan-Hong; Wang, Mei; Khan, Ikhlas A

    2015-10-01

    Ginkgo biloba is one of the most widely sold herbal supplements and medicines in the world. Its popularity stems from having a positive effect on memory and the circulatory system in clinical studies. As ginkgo popularity increased, non-proprietary extracts were introduced claiming to have a similar phytochemical profile as the clinically tested extracts. The standardized commercial extracts of G. biloba leaf used in ginkgo supplements contain not less than 6% sesquiterpene lactones and 24% flavonol glycosides. While sesquiterpene lactones are unique constituents of ginkgo leaf, the flavonol glycosides are found in many other botanical extracts. Being a high value botanical, low quality ginkgo extracts may be subjected to adulteration with flavonoids to meet the requirement of 24% flavonol glycosides. Chemical analysis by ultra high performance liquid chromatography-mass spectrometry revealed that adulteration of ginkgo leaf extracts in many of these products is common, the naturally flavonol glycoside-rich extract being spiked with pure flavonoids or extracts made from another flavonoid-rich material, such as the fruit/flower of Japanese sophora (Styphnolobium japonicum), which also contains the isoflavone genistein. Recently, genistein has been proposed as an analytical marker for the detection of adulteration of ginkgo extracts with S. japonicum. This study confirms that botanically authenticated G. biloba leaf and extracts made therefrom do not contain genistein, and the presence of which even in trace amounts is suggestive of adulteration. In addition to the mass spectrometric approach, a high performance thin layer chromatography method was developed as a fast and economic method for chemical fingerprint analysis of ginkgo samples.

  5. Pharmacokinetic determination of ephedrine in Herba Ephedrae and Wu Tou Tang decoctions in rats using ultra performance liquid chromatography tandem mass spectrometry.

    PubMed

    Zheng, Zhijie; Yan, Tongmeng; Chen, Weiying; Ye, Ling; Tang, Lan; Liu, Zhongqiu

    2012-08-01

    A rapid and sensitive ultra performance liquid chromatography tandem mass spectrometry method was developed and validated for the determination and quantification of ephedrine in rat plasma samples. An Acquity UPLC BEH C18 column (1.7 μm, 2.1 mm × 50 mm) was used for chromatographic separation. Electrospray ionization in the positive mode was used, and the precursor-fragment ion pairs of m/z 166/148 and m/z 289/97 were adopted to characterize ephedrine and testosterone (internal standard), respectively. The method was validated using 10, 100 and 500 ng/mL of ephedrine. It demonstrated adequate levels of precision and accuracy, matrix effect, extraction recovery and stability. Linearity over the concentration range of 0.5-2000 ng/mL was acceptable with a correlation coefficient (r²) better than 0.990. To determine the pharmacokinetic behaviour of this sympathomimetic compound in the Sprague-Dawley rats, ephedrine hydrochloride, Herba Ephedrae single-herb and Wu Tou Tang decoctions were administered orally, and ephedrine hydrochloride was also administered by intravenous injection, and blood samples were collected over 24 h. Ephedrine was measured in plasma and pharmacokinetic parameters were determined by using the standard non-compartmental method and calculated by using Practical Pharmacokinetic Program-Version 87/97. The AUC(0-t) and T(max) values were significantly different (p < 0.05). Ephedrine AUC(0-t) values were significantly lower following the Wu Tou Tang decoction compared to the other oral treatments, suggesting that some components in the decoction may reduce the bioavailability of ephedrine.

  6. Quantification of VX Nerve Agent in Various Food Matrices by Solid-Phase Extraction Ultra-Performance Liquid ChromatographyTime-of-Flight Mass Spectrometry

    DTIC Science & Technology

    2016-04-01

    QUANTIFICATION OF VX NERVE AGENT IN VARIOUS FOOD MATRICES BY SOLID-PHASE EXTRACTION ULTRA-PERFORMANCE...TITLE AND SUBTITLE Quantification of VX Nerve Agent in Various Food Matrices by Solid-Phase Extraction Ultra-Performance Liquid Chromatography... food matrices. The mixed-mode cation exchange (MCX) sorbent and Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) methods were used for

  7. Rapid Quantitative Analysis of Naringenin in the Fruit Bodies of Inonotus vaninii by Two-phase Acid Hydrolysis Followed by Reversed Phase-high Performance Liquid Chromatography-ultra Violet.

    PubMed

    Guohua, Xia; Pan, Ruirong; Bao, Rui; Ge, Yanru; Zhou, Cunshan; Shen, Yuping

    2017-01-01

    Sanghuang is one of mystical traditional Chinese medicines recorded earliest 2000 years ago, that included various fungi of Inonotus genus and was well-known for antitumor effect in modern medicine. Inonotus vaninii is grown in natural forest of Northeastern China merely and used as Sanghuang commercially, but it has no quality control specification until now. This study was to establish a rapid method of two-phase acid hydrolysis followed by reversed phase-high performance liquid chromatography-ultra violet (RP-HPLC-UV) to quantify naringenin in the fruit body of I. vaninii . Sample solution was prepared by pretreatment of raw material in two-phase acid hydrolysis and the hydrolysis technology was optimized. After reconstitution, analysis was performed using RP-HPLC-UV. The method validation was investigated and the naringenin content of sample and comparison were determined. The naringenin was obtained by two-phase acid hydrolysis method, namely, 10.0 g of raw material was hydrolyzed in 200 mL of 1% sulfuric acid aqueous solution (v/v) and 400 mL of chloroform in oil bath at 110°C for 2 h. Good linearity ( r = 0.9992) was achieved between concentration of analyte and peak area. The relative standard deviation (RSD) of precision was 2.47% and the RSD of naringenin contents for repeatability was 3.13%. The accuracy was supported with recoveries at 96.37%, 97.30%, and 99.31%. The sample solution prepared using the proposed method contained higher content of naringenin than conventional method and was stable for 8 h. Due to the high efficiency of sample preparation and high reliability of the HPLC method, it is feasible to use this method for routine analysis of naringenin in the fungus. A convenient two-phase acid hydrolysis was employed to produce naringenin from raw material, and then an efficient and reliable reversed phase-high performance liquid chromatography-ultra violet method was established to monitor naringenin in the fruit bodies of Inonotus vaninii

  8. Selectively Adsorptive Extraction of Phenylarsonic Acids in Chicken Tissue by Carboxymethyl α-Cyclodextrin Immobilized Fe3O4 Magnetic Nanoparticles Followed Ultra Performance Liquid Chromatography Coupled Tandem Mass Spectrometry Detection

    PubMed Central

    Jia, Jing; Zhang, Wei; Wang, Jing; Wang, Peilong; Zhu, Ruohua

    2014-01-01

    Carboxymethyl α-cyclodextrin immobilized Fe3O4 magnetic nanoparticles (CM-α-CD-Fe3O4) were synthesized for the selectively adsorptive extraction of five phenylarsonic acids including p-amino phenylarsonic acid, p-nitro phenylarsonic acid, p-hydroxy phenylarsonic acid, p-acylamino phenylarsonic acid and p-hydroxy-3-nitro phenylarsonic acid in chicken tissue. Using ultra performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS), a highly sensitive analytical method was proposed for the determination of five phenylarsonic acids. It was shown that CM-α-CD-Fe3O4 could extract the five phenylarsonic acids in complex chicken tissue samples with high extraction efficiency. Under the optimal conditions, a high enrichment factor, ranging from 349 to 606 fold, was obtained. The limits of detection (LODs) (at a signal-to-noise ratio of 3) were in the range of 0.05–0.11 µg/kg for the five phenylarsonic acids. The proposed method was applied for the determination of five target phenylarsonic acids in chicken muscle and liver samples. Recoveries for the spiked samples with 0.2 µg/kg, 2.0 µg/kg and 20 µg/kg of each phenylarsonic acids were in the range of 77.2%–110.2%, with a relative standard deviation (RSD) of less than 12.5%. PMID:25215503

  9. [Analysis of sialic acid in infant formulas using ultra performance liquid chromatography-triple quadrupole mass spectrometry].

    PubMed

    Xie, Honglei; Li, Chun; Liu, Ning

    2013-08-01

    The method for analysing sialic acid in infant formulas by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) has been established. Sialic acid in milk was released via acid hydrolysis, and purified by an HLB solid phase extraction cartridge. The UPLC separation was performed on an ACQUITY UPLC BEH HILIC column (50 mm x 2.1 mm, 1.7 microm) utilizing a gradient elution program of acetonitrile and water (containing 0.1% formic acid) as the mobile phases at a flow rate of 0.25 mL/min. Injection volume and column temperature were set at 5 microL and 30 degrees C, respectively. The identification and quantification were achieved by using electrospray ionisation (ESI)-MS/MS in positive ion mode and multiple reaction monitoring (MRM) mode. The linear range was from 0.05 to 5.0 mg/L for sialic acid and the correlation coefficient (R(2)) was greater than 0.99. The average recoveries spiked at the four concentration levels of 0.1, 0.5, 2.5 and 5.0 mg/L ranged between 84.3% and 98.9% with the relative standard deviations from 4.9% to 8.2%. The limit of detection was 0.01 mg/L. Therefore, this method has the characteristics of simple operation, high reproducibility and sensitivity. It can be widely applied to determine the total contents of sialic acid in infant formula, cow milk and human milk.

  10. Evaluation of cannabinoids concentration and stability in standardized preparations of cannabis tea and cannabis oil by ultra-high performance liquid chromatography tandem mass spectrometry.

    PubMed

    Pacifici, Roberta; Marchei, Emilia; Salvatore, Francesco; Guandalini, Luca; Busardò, Francesco Paolo; Pichini, Simona

    2017-08-28

    Cannabis has been used since ancient times to relieve neuropathic pain, to lower intraocular pressure, to increase appetite and finally to decrease nausea and vomiting. The combination of the psychoactive cannabis alkaloid Δ9-tetrahydrocannabinol (THC) with the non-psychotropic alkaloids cannabidiol (CBD) and cannabinol (CBN) demonstrated a higher activity than THC alone. The Italian National Institute of Health sought to establish conditions and indications on how to correctly use nationally produced cannabis to guarantee therapeutic continuity in individuals treated with medical cannabis. The evaluation of cannabinoids concentration and stability in standardized preparations of cannabis tea and cannabis oil was conducted using an easy and fast ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) assay. Extraction efficiency of oil was significantly higher than that of water with respect to the different cannabinoids. This was especially observed in the case of the pharmacologically active THC, CBD and their acidic precursors. Fifteen minutes boiling was sufficient to achieve the highest concentrations of cannabinoids in the cannabis tea solutions. At ambient temperature, a significant THC and CBD decrease to 50% or less of the initial concentration was observed over 3 and 7 days, respectively. When refrigerated at 4 °C, similar decreasing profiles were observed for the two compounds. The cannabinoids profile in cannabis oil obtained after pre-heating the flowering tops at 145 °C for 30 min in a static oven resulted in a complete decarboxylation of cannabinoid acids CBDA and THCA-A. Nevertheless, it was apparent that heat not only decarboxylated acidic compounds, but also significantly increased the final concentrations of cannabinoids in oil. The stability of cannabinoids in oil samples was higher than that in tea samples since the maximum decrease (72% of initial concentration) was observed in THC coming from unheated flowering

  11. Ultra-performance liquid chromatography tandem mass spectrometry method for the determination of AZ66, a sigma receptor ligand, in rat plasma and its application to in vivo pharmacokinetics.

    PubMed

    Jamalapuram, Seshulatha; Vuppala, Pradeep Kumar; Abdelazeem, Ahmed H; McCurdy, Christopher R; Avery, Bonnie A

    2013-08-01

    Methamphetamine abuse continues as a major problem in the USA owing to its powerful psychological addictive properties. AZ66, 3-[4-(4-cyclohexylpiperazine-1-yl)pentyl]-6-fluorobenzo[d]thiazole-2(3H)-one, an optimized sigma receptor ligand, is a promising therapeutic agent against methamphetamine. To study the in vivo pharmacokinetics of this novel sigma receptor ligand in rats, a sensitive ultra-performance liquid chromatography/tandem mass spectrometry (UPLC/MS/MS) method was developed in rat plasma and validated. The developed method requires a small volume of plasma (100 μL) and a simple liquid-liquid extraction. The chromatographic separations were achieved in 3.3 min using an Acquity UPLC BEH Shield RP18 column. The mass spectrophotometric detection was carried out using a Waters Micromass Quattro MicroTM triple-quadrupole system. Multiple reaction monitoring was used for the quantitation with transitions m/z 406 → m/z 181 for AZ66 and m/z 448 → m/z 285 for aripiprazole. The method was validated over a concentration range of 1-3500 ng/mL and the lower limit of quantitation was determined to be 1 ng/mL. Validation of the assay demonstrated that the developed UPLC/MS/MS method was sensitive, accurate and selective for the determination of AZ66 in rat plasma. The present method has been successfully applied to an i.v. pharmacokinetic study in Sprague-Dawley rats. Copyright © 2013 John Wiley & Sons, Ltd.

  12. High-performance liquid chromatography of oligoguanylates at high pH

    NASA Technical Reports Server (NTRS)

    Stribling, R.; Deamer, D. (Principal Investigator)

    1991-01-01

    Because of the stable self-structures formed by oligomers of guanosine, standard high-performance liquid chromatography techniques for oligonucleotide fractionation are not applicable. Previously, oligoguanylate separations have been carried out at pH 12 using RPC-5 as the packing material. While RPC-5 provides excellent separations, there are several limitations, including the lack of a commercially available source. This report describes a new anion-exchange high-performance liquid chromatography method using HEMA-IEC BIO Q, which successfully separates different forms of the guanosine monomer as well as longer oligoguanylates. The reproducibility and stability at high pH suggests a versatile role for this material.

  13. Liquid chromatography-tandem mass spectrometry method for determination of panel of neurotransmitters in cerebrospinal fluid from the rat model for tauopathy.

    PubMed

    Kovac, Andrej; Somikova, Zuzana; Zilka, Norbert; Novak, Michal

    2014-02-01

    Alzheimer's disease (AD) is still being recognized today as an unmet medical need. Currently, there is no cure and early preclinical diagnostic assay available for AD. Therefore much attention is now being directed at the development of novel methods for quantitative determination of AD biomarkers in the cerebrospinal fluid (CSF). Here, we describe the liquid chromatography-tandem mass spectrometry method for determination of 5-hydroxytryptamine (SER), 5-hydroxyindoleacetic acid (5-HIAA), homovanilic acid (HVA), noradrenaline (NADR), adrenaline (ADR), dopamine (DA), glutamic acid (Glu), γ-aminobutyric acid (GABA), 3,4-dihydroxyphenylacetic acid (DOPAC) and histamine (HIS) in cerebrospinal fluid (CSF) from the rat model for human tauopathy. The benzoyl chloride was used as pre-column derivatization reagents. Neurotransmitters and metabolites were analysed on ultra performance liquid chromatography (UPLC) on C18 column in combination with tandem mass spectrometry. The method is simple, highly sensitive and showed excellent linearity with regression coefficients higher than 0.99. The accuracy was in a range of 93-113% for all analytes. The inter-day precision (n=5 days), expressed as %RSD, was in a range 2-10% for all analytes. Using this method we detected significant changes of CSF levels of two important neurotransmitters/metabolites, ADR and 5-HIAA, which correlates with progression of neurodegeneration in our animal model. © 2013 Published by Elsevier B.V.

  14. Determination of sedative hypnotics in sewage sludge by pressurized liquid extraction with high-performance liquid chromatography and tandem mass spectrometry.

    PubMed

    Arbeláez, Paula; Granados, Judith; Borrull, Francesc; Marcé, Rosa Maria; Pocurull, Eva

    2014-12-01

    This paper describes a method for the determination of eight sedative hypnotics (benzodiazepines and barbiturates) in sewage sludge using pressurized liquid extraction and liquid chromatography with tandem mass spectrometry. Pressurized liquid extraction operating conditions were optimized and maximum recoveries were reached using methanol under the following operational conditions: 100ºC, 1500 psi, extraction time of 5 min, one extraction cycle, flush volume of 60% and purge time of 120 s. Pressurized liquid extraction recoveries were higher than 88% for all the compounds except for carbamazepine (55%). The repeatability and reproducibility between days, expressed as relative standard deviation (n = 5), were lower than 6 and 10%, respectively. The detection limits for all compounds were lower than 12.5 μg/kg of dry weight. The method was applied to determine benzodiazepines and barbiturates in sewage sludge from urban sewage treatment plants, and carbamazepine showed the highest concentration (7.9-18.9 μg/kg dry weight). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Rapid and automated analysis of aflatoxin M1 in milk and dairy products by online solid phase extraction coupled to ultra-high-pressure-liquid-chromatography tandem mass spectrometry.

    PubMed

    Campone, Luca; Piccinelli, Anna Lisa; Celano, Rita; Pagano, Imma; Russo, Mariateresa; Rastrelli, Luca

    2016-01-08

    This study reports a fast and automated analytical procedure for the analysis of aflatoxin M1 (AFM1) in milk and dairy products. The method is based on the simultaneous protein precipitation and AFM1 extraction, by salt-induced liquid-liquid extraction (SI-LLE), followed by an online solid-phase extraction (online SPE) coupled to ultra-high-pressure-liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis to the automatic pre-concentration, clean up and sensitive and selective determination of AFM1. The main parameters affecting the extraction efficiency and accuracy of the analytical method were studied in detail. In the optimal conditions, acetonitrile and NaCl were used as extraction/denaturant solvent and salting-out agent in SI-LLE, respectively. After centrifugation, the organic phase (acetonitrile) was diluted with water (1:9 v/v) and purified (1mL) by online C18 cartridge coupled with an UHPLC column. Finally, selected reaction monitoring (SRM) acquisition mode was applied to the detection of AFM1. Validation studies were carried out on different dairy products (whole and skimmed cow milk, yogurt, goat milk, and powder infant formula), providing method quantification limits about 25 times lower than AFM1 maximum levels permitted by EU regulation 1881/2006 in milk and dairy products for direct human consumption. Recoveries (86-102%) and repeatability (RSD<3, n=6) meet the performance criteria required by EU regulation N. 401/2006 for the determination of the levels of mycotoxins in foodstuffs. Moreover, no matrix effects were observed in the different milk and dairy products studied. The proposed method improves the performance of AFM1 analysis in milk samples as AFM1 determination is performed with a degree of accuracy higher than the conventional methods. Other advantages are the reduction of sample preparation procedure, time and cost of the analysis, enabling high sample throughput that meet the current concerns of food safety and the public

  16. Development and validation of ultra-high performance supercritical fluid chromatography method for determination of illegal dyes and comparison to ultra-high performance liquid chromatography method.

    PubMed

    Khalikova, Maria A; Šatínský, Dalibor; Solich, Petr; Nováková, Lucie

    2015-05-18

    A novel simple, fast and efficient ultra-high performance supercritical fluid chromatography (UHPSFC) method was developed and validated for the separation and quantitative determination of eleven illegal dyes in chili-containing spices. The method involved a simple ultrasound-assisted liquid extraction of illegal compounds with tetrahydrofuran. The separation was performed using a supercritical fluid chromatography system and CSH Fluoro-Phenyl stationary phase at 70°C. The mobile phase was carbon dioxide and the mixture of methanol:acetonitrile (1:1, v/v) with 2.5% formic acid as an additive at the flow rate 2.0 mL min(-1). The UV-vis detection was accomplished at 500 nm for seven compounds and at 420 nm for Sudan Orange G, Butter Yellow, Fast Garnet GBC and Methyl Red due to their maximum of absorbance. All eleven compounds were separated in less than 5 min. The method was successfully validated and applied using three commercial samples of chili-containing spices - Chili sauce (Indonesia), Feferony sauce (Slovakia) and Mojo sauce (Spain). The linearity range of proposed method was 0.50-9.09 mg kg(-1) (r ≥ 0.995). The detection limits were determined as signal to noise ratio of 3 and were ranged from 0.15 mg kg(-1) to 0.60 mg kg(-1) (1.80 mg kg(-1) for Fast Garnet) for standard solution and from 0.25 mg kg(-1) to 1.00 mg kg(-1) (2.50 mg kg(-1) for Fast Garnet, 1.50 mg kg(-1) for Sudan Red 7B) for chili-containing samples. The recovery values were in the range of 73.5-107.2% and relative standard deviation ranging from 0.1% to 8.2% for within-day precision and from 0.5% to 8.8% for between-day precision. The method showed potential for being used to monitor forbidden dyes in food constituents. The developed UHPSFC method was compared to the UHPLC-UV method. The orthogonality of Sudan dyes separation by these two methods was demonstrated. Benefits and drawbacks were discussed showing the reliability of both methods for monitoring of studied illegal dyes in real

  17. Rapid residue analysis of oxathiapiprolin and its metabolites in typical Chinese soil, water, and sediments by a modified quick, easy, cheap, effective, rugged, and safe method with ultra high performance liquid chromatography and tandem mass spectrometry.

    PubMed

    Ju, Chao; Dong, Fengshou; Liu, Xingang; Wu, Xiaohu; Zhao, Huanhuan; Zheng, Yongquan; Xu, Jun

    2015-03-01

    A sensitive and effective method for the simultaneous determination of residues from a new fungicide, oxathiapiprolin, and its metabolites (IN-E8S72 and IN-WR791) in soil, water, and sediment, was developed using ultra high performance liquid chromatography with tandem mass spectrometry. Three compounds were extracted from water, soil, and sediment by using acetonitrile and different proportions of formic acid aqueous solution (1% v/v for water; 2% v/v for soil; and sediment), and were cleaned with octadecylsilane. The target compounds were determined within 5 min using an electrospray ionization source in the positive mode for oxathiapiprolin and in the negative mode for the two metabolites. The limits of quantification for all the three compounds were 0.1 μg/kg in water and 1 μg/kg in soil and sediment. Recovery studies were performed using three spiked levels (0.1, 1, and 10 μg/kg for water; 1, 10, and 50 μg/kg for soil and sediment). The overall average recoveries ranged from 64.8 to 112.7% with all intra- and interday relative standard deviation values below 19.4 and 19.1%, respectively. The method validation confirmed that the proposed method was convenient and reliable for determining residual oxathiapiprolin and its metabolites in soil, water, and sediments. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Determination of nonylphenol ethoxylate metabolites in vegetables and crops by high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    She, Yongxin; Wang, Jing; Zheng, Yongquan; Cao, Weiqiang; Wang, Rongyan; Dong, Fengshou; Liu, Xingang; Qian, Mingrong; Zhang, Hu; Wu, Liqing

    2012-05-01

    A method has been developed for the simultaneous determination of the concentration of nonylphenol (4-NP), nonylphenol monoethoxylates (NP1EO) and nonylphenol diethoxylates (NP2EO) in vegetables and crops by liquid chromatography-tandem quadrupole mass spectrometry (HPLC-MS/MS). These target compounds were extracted from vegetable and crop samples with acetonitrile, and then the extracts were cleaned using solid phase extraction with graphitised carbon black tandem primary secondary amine (PSA) cartridges. The MS method enabled highly reliable identification by monitoring the corresponding ammonium adduct [M+NH4](+) in the positive mode for NP1EO and NP2EO, and the deprotonated molecule [M-H](-) in the negative mode for 4-NP. Recoveries for the spiked samples ranged from 65% to 118%. The limit of detection (LOD) of 4-NP, NP1EO and NP2EO was 3, 5 and 0.1μgkg(-1), respectively. This method would be useful for the quick and routine detection of the residues of 4-NP, NP1EO and NP2EO in vegetables and crops. Copyright © 2011 Elsevier Ltd. All rights reserved.

  19. Countercurrent chromatography separation of saponins by skeleton type from Ampelozizyphus amazonicus for off-line ultra-high-performance liquid chromatography/high resolution accurate mass spectrometry analysis and characterisation.

    PubMed

    de Souza Figueiredo, Fabiana; Celano, Rita; de Sousa Silva, Danila; das Neves Costa, Fernanda; Hewitson, Peter; Ignatova, Svetlana; Piccinelli, Anna Lisa; Rastrelli, Luca; Guimarães Leitão, Suzana; Guimarães Leitão, Gilda

    2017-01-20

    Ampelozizyphus amazonicus Ducke (Rhamnaceae), a medicinal plant used to prevent malaria, is a climbing shrub, native to the Amazonian region, with jujubogenin glycoside saponins as main compounds. The crude extract of this plant is too complex for any kind of structural identification, and HPLC separation was not sufficient to resolve this issue. Therefore, the aim of this work was to obtain saponin enriched fractions from the bark ethanol extract by countercurrent chromatography (CCC) for further isolation and identification/characterisation of the major saponins by HPLC and MS. The butanol extract was fractionated by CCC with hexane - ethyl acetate - butanol - ethanol - water (1:6:1:1:6; v/v) solvent system yielding 4 group fractions. The collected fractions were analysed by UHPLC-HRMS (ultra-high-performance liquid chromatography/high resolution accurate mass spectrometry) and MS n . Group 1 presented mainly oleane type saponins, and group 3 showed mainly jujubogenin glycosides, keto-dammarane type triterpene saponins and saponins with C 31 skeleton. Thus, CCC separated saponins from the butanol-rich extract by skeleton type. A further purification of group 3 by CCC (ethyl acetate - ethanol - water (1:0.2:1; v/v)) and HPLC-RI was performed in order to obtain these unusual aglycones in pure form. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Matrix effect on the determination of synthetic corticosteroids and diuretics by liquid chromatography-tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    Dikunets, M. A.; Appolonova, S. A.; Rodchenkov, G. M.

    2009-04-01

    This work presents a high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) procedure for selective and reliable screening of corticosteroids and diuretics in human urine. Sample preparation included the extraction, evaporation of the organic extract under nitrogen, and solution of the dry residue. The extract was analyzed by HPLC combined with tandem mass spectrometry using electro-spraying ionization at atmospheric pressure with negative ion recording. The mass spectra of all compounds were recorded, and the characteristic ions, retention times, and detection limits were determined. The procedure was validated by evaluating the degree of the matrix suppression of ionization, extraction of analytes from human biological liquid, and the selectivity and specificity of determination.

  1. Characterization of vitamin D3 metabolites using continuous-flow fast atom bombardment tandem mass spectrometry and high-performance liquid chromatography.

    PubMed

    Yeung, B; Vouros, P; Reddy, G S

    1993-08-13

    A mass spectrometric method for the detection of vitamin D3 metabolites is described. This method involves the derivatization of the metabolites by cycloaddition with 4-phenyl-1,2,4-triazoline-3,5-dione, followed by their characterization by continuous-flow fast atom bombardment (CF-FAB) tandem mass spectrometry (MS-MS) and high-performance liquid chromatography (HPLC). Using HPLC, this derivatization has been shown to increase the UV detectability of 25-hydroxyvitamin D3 by about 5-fold. The FAB spectra of the adducts are dominated by peaks corresponding to a protonated molecule and a fragment ion derived in part from the loss of the side chain. Multiple reaction monitoring (MRM) of this transition by MS-MS may be utilized for trace level analysis of vitamin D metabolites. Sample introduction by flow injection yields detection limits in the low nanogram to high picogram range, whereas the use of on-line capillary LC has been found to decrease the detection limits to the low picogram level.

  2. A strategy for screening antioxidants in Ginkgo biloba extract by comprehensive two-dimensional ultra high performance liquid chromatography.

    PubMed

    Guo, Ru-Zhou; Liu, Xin-Guang; Gao, Wen; Dong, Xin; Fanali, Salvatore; Li, Ping; Yang, Hua

    2015-11-27

    Recently, screening of bioactive compounds by on-line ultra-high performance liquid chromatography (UHPLC) draws increasing attentions for the advantages of rapidity and intuition. Nevertheless, most on-line methods were limited to the shortcoming like low resolution and peak capacity, which could interfere the active ingredient identification. Comprehensive two-dimensional UHPLC (LC×LC) has revealed to be a powerful tool to separate complex mixtures. Herein, a strategy based on LC×LC analysis coupled with pre-column 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay was proposed to screen the antioxidants from the extract of Ginkgo biloba (EGB). A total of 61 compounds were identified in EGB, and 25 of them showed appreciable radical scavenging capacity. This work may offer pharmacodynamics base for further research about EGB, also the strategy is likelihood to be applied in screening antioxidant in other herbal medicine. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Ultra-high pressure liquid chromatography-tandem mass spectrometry method for the determination of omarigliptin in rat plasma and its application to a pharmacokinetic study in rats.

    PubMed

    Li, Meng-Fang; Hu, Xiao-Xia; Ma, Ai-Qun

    2017-10-01

    Omarigliptin is a novel long-acting dipeptidyl peptidase-4 inhibitor used for the treatment of type 2 diabetes. In this work, a sensitive and selective ultra-high pressure liquid chromatography tandem mass spectrometry method was developed and validated for the determination of omarigliptin in rat plasma. Sample preparation was performed by protein precipitation with acetonitrile. Chromatographic separation of analytes was achieved on an RRHD Eclipse Plus C18 column (2.1 × 50 mm, 1.8 μm), using gradient mobile phase (0.1% formic acid-acetonitrile) at a flow rate of 0.4 mL/min. Detection was performed in multiple reaction monitoring mode, with target fragment ions m/z 399.1 → 152.9 for omarigliptin and m/z 237.1 → 194 for the internal standard. The total run time was 4 min. Retention time of omarigliptin and internal standard was 1.25 and 2.12 min, respectively. Relative standard deviation (%) of the intra- and inter-day precision was below 10.0%, and accuracy was between 97.9% and 105.3%. Calibration curve was established over the range 2-5000 ng/mL with good linearity. The lower limit of quantification and limit of detection of omarigliptin were 2 and 0.25 ng/mL, respectively. Mean recoveries were in the range 87.3-95.1% for omarigliptin. No matrix effect was observed in this method. This novel method has been successfully applied to a pharmacokinetic study of omarigliptin in rats. The absolute bioavailability of omarigliptin was identified as high as 87.31%. Copyright © 2017 John Wiley & Sons, Ltd.

  4. Simultaneous Determination of Black Tea-Derived Catechins and Theaflavins in Tissues of Tea Consuming Animals Using Ultra-Performance Liquid-Chromatography Tandem Mass Spectrometry

    PubMed Central

    Ganguly, Souradipta; G., Taposh Kumar; Mantha, Sudarshan

    2016-01-01

    The bioavailability, tissue distribution and metabolic fate of the major tea polyphenols, catechins and theaflavins as well as their gallated derivatives are yet to be precisely elucidated on a single identification platform for assessment of their relative bioefficacy in vivo. This is primarily due to the lack of suitable analytical tools for their simultaneous determination especially in an in vivo setting, which continues to constrain the evaluation of their relative health beneficiary potential and therefore prospective therapeutic application. Herein, we report a rapid and sensitive Ultra-Performance Liquid Chromatography Tandem Mass Spectrometry (UPLC-MS/MS) based method for the simultaneous determination of the major catechins and theaflavins in black tea infusions as well as in different vital tissues and body fluids of tea-consuming guinea pigs. This method allowed efficient separation of all polyphenols within seven minutes of chromatographic run and had a lower limit of quantification (LLOQ) of ~5 ng/ml. Using this method, almost all bioactive catechins and theaflavins could be simultaneously detected in the plasma of guinea pigs orally administered 5% black tea for 14 days. Our method could further detect the majority of these polyphenols in the lung and kidney as well as identify the major catechin metabolites in the urine of the tea-consuming animals. Overall, our study presents a novel tool for simultaneous detection and quantitation of both catechins and theaflavins in a single detection platform that could potentially enable precise elucidation of their relative bioavailability and bioefficacy as well as true health beneficiary potential in vivo. Such information would ultimately facilitate the accurate designing of therapeutic strategies utilizing high efficacy formulations of tea polyphenols for effective mitigation of oxidative damage and inflammation in humans as well as prevention of associated diseases. PMID:27695123

  5. Simultaneous determination of sulfonamides, penicillins and coccidiostats in pork by high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Nebot, C; Regal, P; Miranda, J; Cepeda, A; Fente, C

    2012-05-01

    Veterinary drugs are widely and legally used to treat and prevent disease in livestock. However, drugs are also used illegally as growth-promoting agents. To protect the health of consumers, maximum residue limits (MRL) in food of animal origin have been established and are listed in Regulation 37/2010. According to this regulation, more than 300 drugs need to be controlled regularly in laboratories for residues of veterinary drugs. A cost-effective analytical method is very important and explains why the development of multi-residual methods is becoming popular in laboratories. The aim of this work is to describe a simple, rapid and economical high-performance liquid chromatography-tandem mass spectrometry method for the simultaneous identification and quantification of 21 veterinary drugs in pork muscle samples. The sample clean-up procedure is performed with acidified dichloromethane and does not require solid phase extraction. The method is applicable to nine sulfonamides and seven coccidiostats identified within 36 min. Calculated relevant validation parameters such as recoveries (from 72.to 126 %), intra-precision and intermediate precision (relative standard deviation below 40 %) and decision limits (below 7 µg Kg(-1)) were within acceptable range and in compliance with the requirements of Commission Decision 2002/657/EC. © The Author [2012]. Published by Oxford University Press. All rights reserved.

  6. Simultaneous determination and qualitative analysis of six types of components in Naoxintong capsule by miniaturized matrix solid-phase dispersion extraction coupled with ultra high-performance liquid chromatography with photodiode array detection and quadrupole time-of-flight mass spectrometry.

    PubMed

    Wang, Huilin; Jiang, Yan; Ding, Mingya; Li, Jin; Hao, Jia; He, Jun; Wang, Hui; Gao, Xiu-Mei; Chang, Yan-Xu

    2018-02-03

    A simple and effective sample preparation process based on miniaturized matrix solid-phase dispersion was developed for simultaneous determination of phenolic acids (gallic acid, chlorogenic acid, ferulic acid, 3,5-dicaffeoylqunic acid, 1,5-dicaffeoylqunic acid, rosmarinic acid, lithospermic acid, and salvianolic acid B), flavonoids (kaempferol-3-O-rutinoside, calycosin, and formononetin), lactones (ligustilide and butyllidephthalide), monoterpenoids (paeoniflorin), phenanthraquinones (cryptotanshinone), and furans (5-hydroxymethylfurfural) in Naoxintong capsule by ultra high-performance liquid chromatography. The optimized condition was that 25 mg Naoxintong powder was blended homogeneously with 100 mg Florisil PR for 4 min. One milliliter of methanol/water (75:25, v/v) acidified by 0.05% formic acid was selected to elute all components. It was found that the recoveries of the six types of components ranged from 61.36 to 96.94%. The proposed miniaturized matrix solid-phase dispersion coupled with ultra high-performance liquid chromatography was successfully applied to simultaneous determination of the six types of components in Naoxintong capsules. The results demonstrated that the proposed miniaturized matrix solid-phase dispersion coupled with ultra high-performance liquid chromatography could be used as an environmentally friendly tool for the extraction and determination of multiple bioactive components in natural products. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Determination of Flavonoids and Anthocyanins in Nitraria tangutorum by High Performance Liquid Chromatography Coupled with Tandem Mass Spectrometry.

    PubMed

    Zhe, Gao; Ying-Chun, Wang; Yan-Xu, Chang

    2016-01-01

    Using high-performance liquid chromatography coupled with diode array detection and electrospray ionization tandem mass spectrometry (HPLC-DAD-MSn) method, qualitative and quantitative analysis of flavonoids of stems, leaves, fruits and seeds, and anthocyanidin of fresh fruits in Nitraria tangutorum were performed. A total of 14 flavonoid components were identified from the seeds of N. tangutorum including three quercetin derivatives, three kaempferol derivatives, and eight isorhamnetin derivatives. A total of 12, 10, and 7 flavonoid components were identified from leaves, stems, and fruits of N. tangutorum, respectively; all were present in seeds also. The total content of flavonoids in leaves was the highest, up to 42.43 mg/g·dry weight. A total of 12 anthocyanidin components were identified from the fresh fruits of N. tangutorum, belonging to five anthocyanidin. The total content of anthocyanidin in fresh fruits was up to 45.83 mg/100 g· fresh weight, of which the acylated anthocyanidin accounted for 65.7%. The HPLC-DAD-MS(n) method can be operated easily, rapidly, and accurately, and is feasible for qualitative and quantitative analysis of flavone glycosides in N. tangutorum.

  8. Determination of three estrogens and bisphenol A by functional ionic liquid dispersive liquid-phase microextraction coupled with ultra-high performance liquid chromatography and ultraviolet detection.

    PubMed

    Jiang, Yuehuang; Tang, Tingting; Cao, Zhen; Shi, Guoyue; Zhou, Tianshu

    2015-06-01

    A hydroxyl-functionalized ionic liquid, 1-hydroxyethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, was employed in an improved dispersive liquid-phase microextraction method coupled with ultra high performance liquid chromatography for the enrichment and determination of three estrogens and bisphenol A in environmental water samples. The introduced hydroxyl group acted as the H-bond acceptor that dispersed the ionic liquid effectively in the aqueous phase without dispersive solvent or external force. Fourier transform infrared spectroscopy indicated that the hydroxyl group of the cation of the ionic liquid enhanced the combination of extractant and analytes through the formation of hydrogen bonds. The improvement of the extraction efficiency compared with that with the use of alkyl ionic liquid was proved by a comparison study. The main parameters including volume of extractant, temperature, pH, and extraction time were investigated. The calibration curves were linear in the range of 5.0-1000 μg/L for estrone, estradiol, and bisphenol A, and 10.0-1000 μg/L for estriol. The detection limits were in the range of 1.7-3.4 μg/L. The extraction efficiency was evaluated by enrichment factor that were between 85 and 129. The proposed method was proved to be simple, low cost, and environmentally friendly for the determination of the four endocrine disruptors in environmental water samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Identification of kinetin and kinetin riboside in coconut (Cocos nucifera L.) water using a combined approach of liquid chromatography-tandem mass spectrometry, high performance liquid chromatography and capillary electrophoresis.

    PubMed

    Ge, Liya; Yong, Jean Wan Hong; Goh, Ngoh Khang; Chia, Lian Sai; Tan, Swee Ngin; Ong, Eng Shi

    2005-12-27

    Kinetin (free base and riboside), which was assumed by many scientists to be a synthetic cytokinin plant growth hormone, has been detected for the first time in the endosperm liquid of fresh young coconut fruits ("coconut water"). To facilitate the study, we developed a sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the identification and quantification of kinetin and kinetin riboside in purified coconut water extract sample. Following a solid-phase extraction of cytokinins in coconut water using C18 columns, the samples were further purified by Oasis MCX columns and analyzed by LC-MS/MS for kinetin and kinetin riboside. Detection by mass spectrometry was carried out using selected reaction monitoring (SRM) mode, by identifying the putative kinetin and kinetin riboside based on their characteristic fragments. Based on a signal-to-noise ratio of 3, the limits of detection in SRM mode were 0.02 microM and 0.005 microM for kinetin and kinetin riboside, respectively. Furthermore, optimal conditions for a baseline chromatographic separation of 18 cytokinin standards by high performance liquid chromatography (HPLC) were developed. The HPLC method had been employed for the confirmation and further fractionation of kinetin in coconut water extracts. The confirmation and fractionation of kinetin riboside was carried out using a further modified HPLC program due to the presence of other interfering material(s) in the sample matrix. Finally, fractions of putative kinetin and kinetin riboside collected from HPLC eluate of coconut water sample were further authenticated by independent capillary zone electrophoresis (CZE) experiment.

  10. [Simultaneous determination of 6 forbidden colorants in cosmetics by high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Lin, Weixuan; Sun, Xingquan; Zhao, Xuerong; Xu, Wei; Guo, Guiyuan

    2012-05-01

    A method of high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) has been established for the simultaneous determination of six forbidden colorants including Sudan IV, Acid Violet 49, Sudan Blue 2, Solvent Red 49, Basic Violet 1 and Pigment Orange 5 in cream and powdery matrix cosmetics. The samples were extracted with ethanol-acetonitrile (3:2, v/v) solution by ultrasonic technique for 20 min, then centrifuged for purification and enriched by nitrogen blowing sequentially. The analytes were isolated on a Luna C18 column (150 mm x 2.1 mm, 5 microm) by gradient elution with methanol and 10 mmol/L ammonium acetate as the mobile phases, and detected by MS/MS in the multiple reaction monitoring (MRM) mode. The qualitative analysis was based on the retention time and the relative abundance ratio of the characteristic ions, and the quantitative analysis on calibration curve method. The results showed that the limits of quantification (LOQ, S/N= 10) of the six colorants ranged from 0.1 to 10 microg/kg and the average recoveries were from 86.67% to 98.22% with the relative standard deviations (RSDs) from 4.01% to 7.01%. The method is simple and rapid with high sensitivity and good reproducibility, and suitable for the determination of the six forbidden colorants in cosmetics.

  11. [Determination of gossypol in edible vegetable oil with high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Zhang, Wenhua; Huang, Chaoqun; Xie, Wen; Shen, Li

    2014-06-01

    A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for the determination of gossypol in edible vegetable oil. The sample was extracted with ethyl alcohol by vortex-excited oscillation. The extract was cleaned up by 0.22 microm filter membrane and centrifuged for 5 min at 4 000 r/min after standing in a fridge at 4 degrees C for 30 min. The compound was separated on a C18 column (100 mm x 2.1 mm, 3.5 microm) with acetonitrile and 1% (v/v) formic acid aqueous solution as mobile phase. The detection of gossypol was carried out by LC-MS/MS with positive electrospray ionization under multiple reaction monitoring (MRM) mode using external standard method. The limits of quantification (S/N > 10) of gossypol in edible vegetable oil was 1 mg/kg. The recoveries were from 87.4% to 100% at the spiked levels of 1, 2, 200 mg/kg of gossypol in edible vegetable oil with the relative standard deviations (RSDs) between 3.9% and 12.2%. The method, with high sensitivity, good precision and high recovery, was suitable for the confirmation and quantification of gossypol residue in edible vegetable oil.

  12. Identification of cardiac glycosides in fractions from Periploca forrestii by high-performance liquid chromatography/diode-array detection/electrospray ionization multi-stage tandem mass spectrometry and liquid chromatography/nuclear magnetic resonance.

    PubMed

    Li, Yong; Wu, Xianfu; Li, Jianbei; Wang, Yinghong; Yu, Shishan; Lv, Haining; Qu, Jing; Abliz, Zeper; Liu, Jing; Liu, Yuanyan; Du, Dan

    2010-02-01

    Cardiac glycosides are a class of naturally occurring compounds that are characterized by some interesting biological activities and are widely distributed in the plant kingdom and can also be found in some animals. There is an interest in the chemical characterization of these molecules due to their toxicity and their use in medicines. In the study reported here, a combination of electrospray ionization tandem mass spectrometry with high-performance liquid chromatography equipped with diode-array detector (HPLC-DAD/ESI-MS(n)), and hyphenation to both liquid chromatography and nuclear magnetic resonance spectroscopy (HPLC/NMR) were utilized for the on-line analyses of cardiac glycosides from Periploca forrestii. The fragmentation patterns and (1)H NMR spectra of nine isolated cardiac glycosides were investigated; their fragmentation rules and (1)H NMR spectral characteristics were summarized and applied to the structural identification of similar constituents in fractions from P. forrestii. As a result, a total of nine trace cardiac glycosides were tentatively determined by analyses of accurate molecular masses, representative fragment ions and characteristic (1)H NMR signals provided by HPLC/high-resolution mass spectrometry (HRMS), HPLC-DAD/ESI-MS(n) and HPLC/(1)H NMR experiments, respectively. Of these, eight (2-9) are new compounds and one (1) is reported from P. forrestii for the first time. Results of the present study can benefit the rapid identification and targeted isolation of new cardiac glycosides from crude plant extracts. 2009 Elsevier B.V. All rights reserved.

  13. Validated ultra-performance liquid chromatography-tandem mass spectrometry method for analyzing LSD, iso-LSD, nor-LSD, and O-H-LSD in blood and urine.

    PubMed

    Chung, Angela; Hudson, John; McKay, Gordon

    2009-06-01

    The Royal Canadian Mounted Police Forensic Science and Identification Services was looking for a confirmatory method for lysergic acid diethylamide (LSD). As a result, an ultra-performance liquid chromatography-tandem mass spectrometry method was validated for the confirmation and quantitation of LSD, iso-LSD, N-demethyl-LSD (nor-LSD), and 2-oxo-3-hydroxy-LSD (O-H-LSD). Relative retention time and ion ratios were used as identification parameters. Limits of detection (LOD) in blood were 5 pg/mL for LSD and iso-LSD and 10 pg/mL for nor-LSD and O-H-LSD. In urine, the LOD was 10 pg/mL for all analytes. Limits of quantitation (LOQ) in blood and urine were 20 pg/mL for LSD and iso-LSD and 50 pg/mL for nor-LSD and O-H-LSD. The method was linear, accurate, and precise from 10 to 2000 pg/mL in blood and 20 to 2000 pg/mL in urine for LSD and iso-LSD and from 20 to 2000 pg/mL in blood and 50 to 2000 pg/mL in urine for nor-LSD and O-H-LSD with a coefficient of determination (R(2)) > or = 0.99. The method was applied to blinded biological control samples and biological samples taken from a suspected LSD user. This is the first reported detection of O-H-LSD in blood from a suspected LSD user.

  14. [Analysis of sulfonamids and their metabolites in drinking water by high Performance liquid chromatography tandem mass spectrometry].

    PubMed

    Wang, Shuo; Li, Shuming; Zhang, Xiangming; Wei, Yunfang; Zhang, Meiyun; Zhang, Jing

    2015-07-01

    To develop a comprehensive method for simultaneous analysis of sulfonamides and their metabolites in drinking water by high performance liquid chromatography tandem mass spectrometry (LC-MS/MS). Different solid-phase extraction columns were compared with respect to the recovery of target drugs from drinking water. The drinking water samples were adjusted to 3 by HCl and purified by a mix mode cation-ion exchange solid-phase extraction (SPE), following determination using LG-MS/MS. A total of 21 sulfonamides were separated by a C15 column (2.1 mm x 100 mm, 1.7 µm) and analyzed under positive ion mode with multi-reaction monitoring. The matrix-matched external standard calibration was used for quantification. The method quantification limits for 21 analytes were 0.03-0.63 ng/L with overall recoveries of 50.1%-114.9%, and the relative standard deviations less than 20%. The method was finally used to analyze sulfonamides in drinking water in Beijing, and 5 target compounds (sulfadiazine, sulfathiazole, sulfapyridine, trimethoprim and sulfamethazine) were detected at a concentration range of 0.08-32.54 ng/L. This method could be applied in simultaneous analysis of sulfonamides and their metabolites in drinking water samples.

  15. Characterization of alkaloids in Sophora flavescens Ait. by high-performance liquid chromatography-electrospray ionization tandem mass spectrometry.

    PubMed

    Liu, Guoqiang; Dong, Jing; Wang, Hong; Hashi, Yuki; Chen, Shizhong

    2011-04-05

    Sophora flavescens Ait., a well-known Chinese herbal medicine, is widely used in clinical practice for the treatment of viral hepatitis, cancer, gastrointestinal hemorrhage, and skin diseases. This paper is the first report on a method based on the combined use of high-performance liquid chromatography, photodiode array detection, and electrospray ionization tandem mass spectrometry for the comprehensive and systematic separation and characterization of bioactive alkaloids in Sophora flavescens Ait. A total of 22 constituents were identified on the basis of the extracted ion chromatograms for different [M+H](+) ions of the alkaloids present in S. flavescens Ait. Among these, 5 constituents were unambiguously identified by comparing the experimental data on their retention times and MS(n) spectra with those of the authentic compounds, and 17 other constituents were tentatively identified on the basis of their MS(n) fragmentation behaviors and/or molecular weight information from literatures. Furthermore, some characteristic fragmentation pathways of the alkaloids in S. flavescens Ait. were detected and examined. This information may be useful for characterizing the bioactive alkaloids present in S. flavescens Ait. and for possible applications in formulations. Copyright © 2010 Elsevier B.V. All rights reserved.

  16. Dispersive liquid-liquid microextraction based on solidification of floating organic droplet followed by high-performance liquid chromatography with ultraviolet detection and liquid chromatography-tandem mass spectrometry for the determination of triclosan and 2,4-dichlorophenol in water samples.

    PubMed

    Zheng, Cao; Zhao, Jing; Bao, Peng; Gao, Jin; He, Jin

    2011-06-24

    A novel, simple and efficient dispersive liquid-liquid microextraction based on solidification of floating organic droplet (DLLME-SFO) technique coupled with high-performance liquid chromatography with ultraviolet detection (HPLC-UV) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed for the determination of triclosan and its degradation product 2,4-dichlorophenol in real water samples. The extraction solvent used in this work is of low density, low volatility, low toxicity and proper melting point around room temperature. The extractant droplets can be collected easily by solidifying it at a lower temperature. Parameters that affect the extraction efficiency, including type and volume of extraction solvent and dispersive solvent, salt effect, pH and extraction time, were investigated and optimized in a 5 mL sample system by HPLC-UV. Under the optimum conditions (extraction solvent: 12 μL of 1-dodecanol; dispersive solvent: 300 of μL acetonitrile; sample pH: 6.0; extraction time: 1 min), the limits of detection (LODs) of the pretreatment method combined with LC-MS/MS were in the range of 0.002-0.02 μg L(-1) which are lower than or comparable with other reported approaches applied to the determination of the same compounds. Wide linearities, good precisions and satisfactory relative recoveries were also obtained. The proposed technique was successfully applied to determine triclosan and 2,4-dichlorophenol in real water samples. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. Analysis of anabolic androgenic steroids as sulfate conjugates using high performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Rzeppa, S; Heinrich, G; Hemmersbach, P

    2015-01-01

    Improvements in doping analysis can be effected by speeding up analysis time and extending the detection time. Therefore, direct detection of phase II conjugates of doping agents, especially anabolic androgenic steroids (AAS), is proposed. Besides direct detection of conjugates with glucuronic acid, the analysis of sulfate conjugates, which are usually not part of the routine doping control analysis, can be of high interest. Sulfate conjugates of methandienone and methyltestosterone metabolites have already been identified as long-term metabolites. This study presents the synthesis of sulfate conjugates of six commonly used AAS and their metabolites: trenbolone, nandrolone, boldenone, methenolone, mesterolone, and drostanolone. In the following these sulfate conjugates were used for development of a fast and easy analysis method based on sample preparation using solid phase extraction with a mixed-mode sorbent and detection by high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS). Validation demonstrated the suitability of the method with regard to the criteria given by the technical documents of the World Anti-Doping Agency (WADA). In addition, suitability has been proven by successful detection of the synthesized sulfate conjugates in excretion urines and routine doping control samples. Copyright © 2015 John Wiley & Sons, Ltd.

  18. Detection of 22 antiepileptic drugs by ultra-performance liquid chromatography coupled with tandem mass spectrometry applicable to routine therapeutic drug monitoring.

    PubMed

    Shibata, Mai; Hashi, Sachiyo; Nakanishi, Haruka; Masuda, Satohiro; Katsura, Toshiya; Yano, Ikuko

    2012-12-01

    The purpose of this study was to develop an ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method of 22 antiepileptics for routine therapeutic monitoring. The antiepileptics used in the analyses were carbamazepine, carbamazepine-10,11-epoxide, clobazam, N-desmethylclobazam, clonazepam, diazepam, N-desmethyldiazepam, ethosuximide, felbamate, gabapentin, lamotrigine, levetiracetam, N-desmethylmesuximide, nitrazepam, phenobarbital, phenytoin, primidone, tiagabine, topiramate, valproic acid, vigabatrin and zonisamide. After protein precipitation of 50 μL plasma with methanol, the supernatant was diluted with water or was evaporated to dryness and reconstituted with mobile phase in the case of benzodiazepines. Separation was achieved on an Acquity UPLC BEH C₁₈ column with a gradient mobile phase of 10 mm ammonium acetate containing 0.1% formic acid and methanol at a flow rate of 0.4 mL/min. An Acquity TQD instrument in multiple reaction monitoring mode with ion mode switching was used for detection. All antiepileptics were detected and quantified within 10 min, with no endogenous interference. All the calibration curves showed good linearity in the therapeutic range (r²  < 0.99). The precision and accuracy values for intra- and inter-assays were within ±15% except for phenobarbital and tiagabine. A good correlation was observed between the concentration of clinical samples measured by the new method described here and the conventional methods. The values of carbamazepine and phenytoin by UPLC-MS/MS were lower than those detected by the immunoassays, which might be caused by the cross-reaction of antibodies with their metabolites. In conclusion, we developed a simple and selective UPLC-MS/MS method suitable for routine therapeutic monitoring of antiepileptics. Copyright © 2012 John Wiley & Sons, Ltd.

  19. [Analysis of microalbuminuria with immunonephelometry and high performance liquid chromatography. Evaluation of new criteria].

    PubMed

    Markó, Lajos; Molnár, Gergo Attila; Wagner, Zoltán; Koszegi, Tamás; Matus, Zoltán; Mohás, Márton; Kuzma, Mónika; Szijártó, István András; Wittmann, István

    2008-01-13

    Hypertension as well as type 2 diabetes mellitus is a major factor in population mortality. Both diseases damage the endothelium, the early sign of which is microalbuminuria, which can be screened by dipstick and can be diagnosed by using immuno-based and high performance liquid chromatography methods. Using high performance liquid chromatography, the non-immunoreactive albumin can be detected as well. The authors aimed at the examination of albuminuria in the case of immunonephelometrically negative patients with high performance liquid chromatography, in diabetic and hypertensive and non-diabetic hypertensive populations. The authors also wanted to compare the present (albumin-creatinine ratio: male: > or =2.5 mg/mmol, female: > or =3.5 mg/mmol) and a new criteria of the Heart Outcomes Prevention Evaluation study (patients without diabetes: immunological method, > or =0.7 mg/mmol; high performance liquid chromatography, > or =3.1 mg/mmol; individuals with diabetes: immunological method, > or =1.4 mg/mmol; high performance liquid chromatography, > or =5.2 mg/mmol) of microalbuminuria. Examination of fresh urines of 469 microalbuminuria negative patients by dipstick were performed by immunonephelometry. Patients, who were microalbuminuria negative by immunonephelometry as well, were further analyzed by high performance liquid chromatography using the Accumintrade mark Kit, based on size-exclusion chromatography. Three times higher albuminuria were found with high performance liquid chromatography than with immunonephelometry. The intraindividual coefficient of variation did not differ in the two methods (37 +/- 31% vs. 40 +/- 31%, p = 0.869; immunonephelometry vs. high performance liquid chromatography; mean +/- standard deviation). Using the present criteria for microalbuminuria, 43% of immunonephelometrically negative patients proved to be microalbuminuric by high performance liquid chromatography. Using the new criteria of the Heart Outcomes Prevention

  20. Quantification of isoflavones in coffee by using solid phase extraction (SPE) and high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS).

    PubMed

    Caprioli, Giovanni; Navarini, Luciano; Cortese, Manuela; Ricciutelli, Massimo; Torregiani, Elisabetta; Vittori, Sauro; Sagratini, Gianni

    2016-09-01

    A new method for extracting isoflavones from espresso coffee (EC) was coupled with high-performance liquid chromatography-tandem mass spectrometry (MS/MS) for the first time to analyse five isoflavones, which included both a glycosilated form, genistin and the aglycons daidzein, genistein, formononetin and biochanin A. Isoflavones were extracted from coffee samples using methanol, stored in a freezer overnight to precipitate proteic or lipidic residues and purified on SPE C18 cartridges before high-performance liquid chromatography-MS/MS analysis. The recovery percentages obtained by spiking the matrix at concentrations of 10 and 100 µg l(-1) with a standard mixture of isoflavones were in the range of 70 to 104%. The limits of detection and limits of quantification were in the range of 0.015-0.3 µg l(-1) and 0.05-1 µg l(-1) , respectively. Once validated, the method was used to analyze the concentrations of isoflavones in six ECs and ten ground coffee samples. Only formononetin and biochanin A were found, and their respective concentrations ranged from 0.36 to 0.41 µg l(-1) and from 0.58 to 3.26 µg l(-1) in ECs and from 0.36 to 4.27 µg kg(-1) and from 0.71 to 3.95 µg kg(-1) in ground coffees. This method confirms the high specificity and selectivity of MS/MS systems for detecting bioactives in complex matrices such as coffee.Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  1. Ultra-high-pressure liquid chromatography tandem mass spectrometry determination of hallucinogenic drugs in hair of psychedelic plants and mushrooms consumers.

    PubMed

    Pichini, Simona; Marchei, Emilia; García-Algar, Oscar; Gomez, Arelis; Di Giovannandrea, Rita; Pacifici, Roberta

    2014-11-01

    A procedure based on ultra-high-pressure liquid chromatography tandem mass spectrometry has been developed for the determination of mescaline, N,N-dimethyltryptamine, psilocin, psilocybin, salvinorin A in hair of consumers of psychedelic vegetal material such peyote or trichocereus cacti, psilocybe mushrooms, Salvia divinorum or psychedelic beverage ayahuasca. After hair washing with methyl alcohol and diethyl ether and subsequent addition of mescaline-d9 and 3,4-methylenedioxypropylamphetamine as internal standards, hair samples were treated with 250μl VMA-T M3 reagent for 1h at 100°C. After cooling, 100μl M3 extract were diluted with 400μl water and a volume of 10μl was injected into chromatographic system. Chromatographic separation was achieved at ambient temperature using a reverse-phase column and a linear gradient elution with two solvents: 0.3% formic acid in acetonitrile and 5mM ammonium formate pH 3. The mass spectrometer was operated in positive ion mode, using multiple reaction monitoring via positive electrospray ionization. The method was linear from the limit of quantification (0.03-0.05ng/mg depending on analyte under investigation) to 10ng/mg hair, with an intra- and inter-assay imprecision and inaccuracy always less than 15% and an analytical recovery between 79.6% and 97.4%, depending on the considered analyte. Using the validated method, mescaline was found in concentration range of 0.08-0.13ng/mg in hair of peyote smokers, 3.2ng salvinorin A per mg hair were determined in hair from a S. divinorum smoker, 5.6ng N,N-dimethyltryptamine per mg hair from an ayahuasca user and finally 0.8ng psilocybin per ng hair of a psilocybe consumer. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Ultra-high-pressure liquid chromatography tandem mass spectrometry determination of antidepressant and anxiolytic drugs in neonatal meconium and maternal hair.

    PubMed

    Pichini, Simona; Cortes, Laura; Marchei, Emilia; Solimini, Renata; Pacifici, Roberta; Gomez-Roig, Mª Dolores; García-Algar, Oscar

    2016-01-25

    A procedure based on ultra-high-pressure liquid chromatography tandem mass spectrometry has been developed for the determination of 22 antidepressant and anxiolytic drugs ad metabolites in the three consecutive maternal hair segments representing the pregnancy trimesters and paired neonatal meconium samples. After hair washing with methyl alcohol and diethyl ether and subsequent addition of internal standards, hair samples were treated with 500 μl VMA-T M3 reagent for 1h at 100 °C. After cooling, 100 μl M3 extract were diluted with 400 μl water and a volume of 10 μl was injected into chromatographic system. Meconium samples were firstly treated with 1 ml methyl alcohol and the organic layer back-extracted twice with 1.5 ml of a mixture of ethylacetate:hexane (80:20, v/v). Chromatographic separation was achieved at ambient temperature using a reverse-phase column and a linear gradient elution with two solvents: 0.3% formic acid in acetonitrile and 5mM ammonium formate pH 3. The mass spectrometer was operated in positive ion mode, using multiple reaction monitoring via positive electrospray ionization. The method was linear from the limit of quantification (0.05-1 ng/mg hair and 5-25 ng/g meconium depending on analyte under investigation;) to 10 ng/mg hair and 1000 ng/g meconium, with an intra- and inter-assay imprecision and inaccuracy always less than 20% and an analytical recovery between 66.6% and 95.3%, depending on the considered analyte and biological matrix. Using the validated method, 7 mothers were found positive to one or more hair segments and 5 meconium samples were found positive to one or more antidepressant and anxiolytic drugs, assessing prenatal exposure to these drugs following maternal consumption in one or more pregnancy trimesters. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Development and validation of an ultra-performance convergence chromatography method for the quality control of Angelica gigas Nakai.

    PubMed

    Kim, Hyo Seon; Chun, Jin Mi; Kwon, Bo-In; Lee, A-Reum; Kim, Ho Kyoung; Lee, A Yeong

    2016-10-01

    Ultra-performance convergence chromatography, which integrates the advantages of supercritical fluid chromatography and ultra high performance liquid chromatography technologies, is an environmentally friendly analytical method that uses dramatically reduced amounts of organic solvents. An ultra-performance convergence chromatography method was developed and validated for the quantification of decursinol angelate and decursin in Angelica gigas using a CSH Fluoro-Phenyl column (2.1 mm × 150 mm, 1.7 μm) with a run time of 4 min. The method had an improved resolution and a shorter analysis time in comparison to the conventional high-performance liquid chromatography method. This method was validated in terms of linearity, precision, and accuracy. The limits of detection were 0.005 and 0.004 μg/mL for decursinol angelate and decursin, respectively, while the limits of quantitation were 0.014 and 0.012 μg/mL, respectively. The two components showed good regression (correlation coefficient (r 2 ) > 0.999), excellent precision (RSD < 2.28%), and acceptable recoveries (99.75-102.62%). The proposed method can be used to efficiently separate, characterize, and quantify decursinol angelate and decursin in Angelica gigas and its related medicinal materials or preparations, with the advantages of a shorter analysis time, greater sensitivity, and better environmental compatibility. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Simultaneous analysis of ten phytohormones in Sargassum horneri by high-performance liquid chromatography with electrospray ionization tandem mass spectrometry.

    PubMed

    Li, Yan; Zhou, Chengxu; Yan, Xiaojun; Zhang, Jinrong; Xu, Jilin

    2016-05-01

    Phytohormones have attracted wide attention due to their important biological functions. However, their detection is still a challenge because of their complex composition, low abundance and diverse sources. In this study, a novel method of high-performance liquid chromatography with electrospray ionization tandem mass spectrometry was developed and validated for the simultaneous determination of ten phytohormones including indole-3-acetic acid, isopentenyladenine, isopentenyl adenosine, trans-zeatin riboside, zeatin, strigolactones, abscisic acid, salicylic acid, gibberellin A3, and jasmonic acid in Sargassum horneri (S. horneri). The phytohormones were extracted from freeze-dried S. horneri with methanol/water/methanoic acid (15:4:1, v/v/v) analyzed on a Hypersil Gold C18 column and detected by electrospray ionization tandem triple quadrupole mass spectrometry in the multiple reaction monitoring mode. The experimental conditions for the extraction and analysis of phytohormones were optimized and validated in terms of reproducibility, linearity, sensitivity, recovery, accuracy, and stability. Distributions of the phytohormones in the stems, blades, and gas bladder of the S. horneri in drift, fixed, and semi-fixed growing states were investigated for the first time. The observed contents of the phytohormones in S. horneri range from not detected to 5066.67 ng/g (fresh weight). Most phytohormones are distributed mainly in the stems of S. horneri in drift and semi-fixed states. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Simultaneous determination of five minor coumarins and flavonoids in Glycyrrhiza uralensis by solid-phase extraction and high-performance liquid chromatography/electrospray ionization tandem mass spectrometry.

    PubMed

    Qiao, Xue; Liu, Chun-Fang; Ji, Shuai; Lin, Xiong-Hao; Guo, De-An; Ye, Min

    2014-02-01

    Minor phenolic compounds in licorice (Glycyrrhiza uralensis) have recently been proved for diverse bioactivities and favorable bioavailability, indicating that they may play an important role in the therapeutic effects or herb-drug interactions of licorice. However, so far, their abundance in licorice remains unknown. In this study, a reliable solid-phase extraction coupled with a high-performance liquid chromatography and diode array detection method was established to determine the minor phenolic compounds in licorice. The analytes were enriched by a three-step solid-phase extraction method, and then separated on a YMC ODS-A column by gradient elution. Five coumarins and flavonoids were identified by electrospray ionization tandem mass spectrometry, and then quantified using high-performance liquid chromatography and diode array detection. The amounts of glycycoumarin, dehydroglyasperin C, glycyrol, licoflavonol, and glycyrin in G. uralensis were 0.81 ± 0.28, 1.25 ± 0.59, 0.20 ± 0.08, 0.12 ± 0.04, and 0.17 ± 0.08 mg/g, respectively. Abundances of these compounds in other Glycyrrhiza species (G. glabra, G. inflata, and G. yunnanesis) were remarkably lower than G. uralensis. Georg Thieme Verlag KG Stuttgart · New York.

  6. Multichannel Detection in High-Performance Liquid Chromatography.

    ERIC Educational Resources Information Center

    Miller, James C.; And Others

    1982-01-01

    A linear photodiode array is used as the photodetector element in a new ultraviolet-visible detection system for high-performance liquid chromatography (HPLC). Using a computer network, the system processes eight different chromatographic signals simultaneously in real-time and acquires spectra manually/automatically. Applications in fast HPLC…

  7. Metabolites identification of harmane in vitro/in vivo in rats by ultra-performance liquid chromatography combined with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    Li, Shuping; Liu, Wei; Teng, Liang; Cheng, Xuemei; Wang, Zhengtao; Wang, Changhong

    2014-04-01

    Harmane, a β-carboline alkaloid with a wide spectrum of pharmacological activities, is naturally present in the human diet, in numerous foodstuffs and in hallucinogenic plants such as Peganum harmala, Banisteriopsis caapi and Tribulus terrestris. However, the precise metabolic fate of harmane remains unknown. In order to know whether harmane is extensively metabolized, a rapid and sensitive method using ultra-performance liquid chromatography combined with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (UPLC/ESI-QTOF-MS) was used to analyze the metabolic profile of harmane in vitro and in vivo in rats. A total of 21 metabolites were identified from the rat liver microsomes and rat liver S9 (9), rat urine (11), feces (16), bile (16), and plasma (10) after a single oral administration of harmane using MetaboLynx™ and MassFragment ™ software tools. It indicated that the biliary and faecal clearance were the major excretion routes for harmane as well as its metabolites. The specific CLogP values combined with different acidic and alkaline mobile phase were helpful and useful for distinguishing N-oxidation and monohydroxylation metabolites. The metabolic transformation pathways of harmane included monohydroxylation, dihydroxylation, N-oxidation, O-glucuronide conjugation, O-sulphate conjugation, and glutathione conjugation. In conclusion, this study showed an insight into the metabolism of harmane. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Liquid chromatography-tandem mass spectrometric assay for the T790M mutant EGFR inhibitor osimertinib (AZD9291) in human plasma.

    PubMed

    Rood, Johannes J M; van Bussel, Mark T J; Schellens, Jan H M; Beijnen, Jos H; Sparidans, Rolf W

    2016-09-15

    A method for the quantitative analysis by ultra-performance liquid chromatography-tandem mass spectrometry of the highly selective irreversible covalent inhibitor of EGFR-TK, osimertinib in human plasma was developed and validated, using pazopanib as an internal standard. The validation was performed in a range from 1 to 1000ng/ml, with the lowest level corresponding to the lower limit of quantitation. Gradient elution was performed on a 1.8μm particle trifunctional bonded C18 column by 1% (v/v) formic acid in water, and acetonitrile as mobile phase. The analyte was detected in the selected reaction monitoring mode of a triple quadrupole mass spectrometer after positive ionization with the heated electrospray interface. Within-day precisions ranged from 3.4 to 10.3%, and between-day precisions from 3.8 to 10.4%, accuracies were 95.5-102.8%. Plasma (either lithium heparin or sodium EDTA) pretreatment was performed by salting-out assisted liquid-liquid extraction using acetonitrile and magnesium sulfate. This method was used to analyze the osimertinib blood plasma levels of five adult patients with metastatic T790M mutated non-small cellular lung carcinoma for therapeutic drug monitoring purposes. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Sensitive determination of D-lactic acid and L-lactic acid in urine by high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Henry, H; Marmy Conus, N; Steenhout, P; Béguin, A; Boulat, O

    2012-04-01

    D-lactic acid in urine originates mainly from bacterial production in the intestinal tract. Increased D-lactate excretion as observed in patients affected by short bowel syndrome or necrotizing enterocolitis reflects D-lactic overproduction. Therefore, there is a need for a reliable and sensitive method able to detect D-lactic acid even at subclinical elevation levels. A new and highly sensitive method for the simultaneous determination of L- and D-lactic acid by a two-step procedure has been developed. This method is based on the concentration of lactic acid enantiomers from urine by supported liquid extraction followed by high-performance liquid chromatography-tandem mass spectrometry. The separation was achieved by the use of an Astec Chirobiotic™ R chiral column under isocratic conditions. The calibration curves were linear over the ranges of 2-400 and 0.5-100 µmol/L respectively for L- and D-lactic acid. The limit of detection of D-lactic acid was 0.125 µmol/L and its limit of quantification was 0.5 µmol/L. The overall accuracy and precision were well within 10% of the nominal values. The developed method is suitable for production of reference values in children and could be applied for accurate routine analysis. Copyright © 2011 John Wiley & Sons, Ltd.

  10. Simultaneous quantification of antimicrobial agents for multidrug-resistant bacterial infections in human plasma by ultra-high-pressure liquid chromatography-tandem mass spectrometry.

    PubMed

    Tsai, I-Lin; Sun, Hsin-Yun; Chen, Guan-Yuan; Lin, Shu-Wen; Kuo, Ching-Hua

    2013-11-15

    Antibiotic-resistant bacterial infection is one of the most serious clinical problems worldwide. Vancomycin, teicoplanin, daptomycin, and colistin are glycopeptide and lipopeptide antibiotics that are frequently used to treat multidrug-resistant bacterial infections. Therapeutic drug monitoring is recommended to ensure both safety and efficacy and to improve clinical outcomes. This study developed a fast, simple, and sensitive ultra-high-pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for the simultaneous determination of the concentrations of these four drugs in human plasma. The sample preparation process includes a simple protein denaturation step using acetonitrile, followed by an 11-fold dilution with 0.1% formic acid. Eight target peaks for the four drugs can be analyzed within 3 min using a Kinetex™ 2.6 μm C18 column. The mass spectrometry parameters were optimized, and two transitions for each target peak were used for multiple reaction monitoring, which provided high sensitivity and specificity. The UHPLC-MS/MS method was validated over clinical concentration ranges. The intra-day and inter-day precisions for the ratio of the peak area of each analyte to the peak area of the internal standard were all below 12.7 and 14.7% relative standard deviations, respectively. The accuracy at low, medium, and high concentrations of the eight target peaks was between 89.3 and 110.7%. The standard curves for the analytes were linear and had coefficients of determination higher than 0.997. The limits of detection were all below 70 ng mL(-1). The use of this method to analyze patient plasma samples confirmed that it is effective for the therapeutic drug monitoring of these four drugs and can be used to improve the therapeutic efficacy and safety of treatment with antibiotics. Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Ultrasensitive quantification of endogenous brassinosteroids in milligram fresh plant with a quaternary ammonium derivatization reagent by pipette-tip solid-phase extraction coupled with ultra-high-performance liquid chromatography tandem mass spectrometry.

    PubMed

    Deng, Ting; Wu, Dapeng; Duan, Chunfeng; Guan, Yafeng

    2016-07-22

    Determination of endogenous brassinosteroids (BRs) in limited sample amount is vital to elucidating their tissue- and even local tissue-specific signaling pathway and physiological effects on plant growth and development. In this work, an ultra-sensitive quantification method was established for endogenous BRs in milligram fresh plant by using pipette-tip solid-phase extraction coupled with ultra-performance liquid chromatography tandem mass spectrometry (PT-SPE-UPLC-MS/MS), in which a quaternary ammonium phenyl boronic acid, 4-borono-N,N,N-trimethylbenzenaminium iodide (BTBA) was first developed for chemical derivatization of BRs. Due to the cationic quaternary ammonium group of BTBA, the ionization efficiencies of the BRs chelates with BTBA (BTBA-BRs) were enhanced by 1190-448785 times, which is the highest response enhancement factor among all derivatization reagents reported for BRs. In addition, PT-SPE packed with C18 sorbent was first used for purifying BRs from plant extracts, so the required sample amount was minimized, and recoveries higher than 91% were achieved. Under the optimized conditions, the minimal detectable amounts (MDA) of five target BRs were in the range of 27-94 amol, and the correlation coefficients (R(2)) were >0.9985 over four orders of magnitude. The relative recoveries of 75.8-104.9% were obtained with the intra- and inter-day relative standard deviations (RSDs) less than 18.7% and 19.6%, respectively. Finally, three BRs were successfully quantified in only 5mg fresh rice plant samples, and 24-epiBL can even be detected in only 0.5mg FW rice leaf segments. It is the first time that the BRs content in sub-milligram fresh plant sample has been quantified. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. An evaluation of sucrose as a possible contaminant in e-liquids for electronic cigarettes by hydrophilic interaction liquid chromatography-tandem mass spectrometry.

    PubMed

    Kubica, Paweł; Wasik, Andrzej; Kot-Wasik, Agata; Namieśnik, Jacek

    2014-05-01

    The influence of sucrose combustion products on smoking and nicotine addiction is still controversial because the presence of the sucrose may be treated as a source of aldehydes and organic acids. In e-liquids used as refills for electronic cigarettes, which are made primarily of poly(propylene glycol), glycerine and ethanol, sucrose may be present at trace levels, and its impact on mainstream smoke formation, and hence on human health and smoking/nicotine addiction is unknown. An analytical method was developed where high-performance liquid chromatography in hydrophilic interaction liquid chromatography mode and tandem mass spectrometry were used for fast and simple determination of sucrose and other saccharides in e-liquids for electronic cigarettes. Minimal effort was required in the sample preparation step, and satisfactory results were obtained, and the sample matrix had an insignificant impact. The chromatographic separation was done using an Ascentis Express OH5 column (150 mm × 2.1 mm, 2.7 μm). The coefficients of variation for within-day precision for three concentrations were 2.4 %, 1.6 % and 2.3 %, and the between-day coefficients of variation for a single concentration were 2.1 %, 2.5 % and 1.7 % measured on the next 3 days. The detection limit was 0.73 μg/g, and the sucrose content in e-liquids ranged from 0.76 to 72.93 μg/g among 37 samples. Moreover, with the method presented it is possible to determine the presence of other saccharides such as fructose, glucose, maltose and lactose. However, only sucrose was found in all samples of e-liquids. The proposed method is rapid, simple and reliable in terms of high-performance liquid chromatography coupled with tandem mass spectrometry.

  13. Bromazepam determination in human plasma by high-performance liquid chromatography coupled to tandem mass spectrometry: a highly sensitive and specific tool for bioequivalence studies.

    PubMed

    Laurito, Tiago L; Mendes, Gustavo D; Santagada, Vincenzo; Caliendo, Giuseppe; de Moraes, Maria Elisabete A; De Nucci, Gilberto

    2004-02-01

    A rapid, sensitive and specific method to quantify bromazepam in human plasma using diazepam as the internal standard (IS) is described. The analyte and the IS were extracted from plasma by liquid-liquid extraction using diethyl ether-hexane (80 : 20, v/v). The extracts were analyzed by high-performance liquid chromatography (HPLC) coupled to electrospray tandem mass spectrometry (MS/MS). Chromatography was performed isocratically on a Genesis C(18) analytical column (100 x 2.1 mm i.d., film thickness 4 microm). The method had a chromatographic run time of 5.0 min and a linear calibration curve over the range 5.0-150 ng ml(-1) (r(2) > 0.9952). The limit of quantification was 5 ng ml(-1). This HPLC/MS/MS procedure was used to assess the bioequivalence of two bromazepam 6 mg tablet formulations (bromazepam from Medley SA Indústria Farmacêutica as the test formulation and Lexotan from Produtos Roche Químico e Farmacêutico SA as the reference formulation). A single 6 mg dose of each formulation was administered to 24 healthy volunteers (12 males and 12 females). The study was conducted using an open, randomized, two-period crossover design with a 3 week washout interval. Since the 90% CI for C(max), AUC(last), AUC(0-240 h) (linear) and AUC((0- infinity )) ratios were all inside the 80-125% interval proposed by the US Food and Drug Administration, it was concluded that the bromazepam formulation from Medley is bioequivalent to the Lexotan formulation for both the rate and the extent of absorption. Copyright 2004 John Wiley & Sons, Ltd.

  14. Multi-component determination and chemometric analysis of Paris polyphylla by ultra high performance liquid chromatography with photodiode array detection.

    PubMed

    Chen, Pei; Jin, Hong-Yu; Sun, Lei; Ma, Shuang-Cheng

    2016-09-01

    Multi-source analysis of traditional Chinese medicine is key to ensuring its safety and efficacy. Compared with traditional experimental differentiation, chemometric analysis is a simpler strategy to identify traditional Chinese medicines. Multi-component analysis plays an increasingly vital role in the quality control of traditional Chinese medicines. A novel strategy, based on chemometric analysis and quantitative analysis of multiple components, was proposed to easily and effectively control the quality of traditional Chinese medicines such as Chonglou. Ultra high performance liquid chromatography was more convenient and efficient. Five species of Chonglou were distinguished by chemometric analysis and nine saponins, including Chonglou saponins I, II, V, VI, VII, D, and H, as well as dioscin and gracillin, were determined in 18 min. The method is feasible and credible, and enables to improve quality control of traditional Chinese medicines and natural products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Sensitive quantification of coixol, a potent insulin secretagogue, in Scoparia dulcis extract using high-performance liquid chromatography combined with tandem mass spectrometry and UV detection.

    PubMed

    Ali, Arslan; Haq, Faraz Ul; Ul Arfeen, Qamar; Sharma, Khaga Raj; Adhikari, Achyut; Musharraf, Syed Ghulam

    2017-10-01

    Diabetes is a major global health problem which requires new studies for its prevention and control. Scoparia dulcis, a herbal product, is widely used for treatment of diabetes. Recent studies demonstrate coixol as a potent and nontoxic insulin secretagog from S. dulcis. This study focuses on developing two quantitative methods of coixol in S. dulcis methanol-based extracts. Quantification of coixol was performed using high-performance liquid chromatography-tandem mass spectrometry (method 1) and high-performance liquid chromatography-ultraviolet detection (method 2) with limits of detection of 0.26 and 11.6 pg/μL, respectively, and limits of quantification of 0.78 and 35.5 pg/μL, respectively. S. dulcis is rich in coixol content with values of 255.5 ± 2.1 mg/kg (method 1) and 220.4 ± 2.9 mg/kg (method 2). Excellent linearity with determination coefficients >0.999 was achieved for calibration curves from 10 to 7500 ng/mL (method 1) and from 175 to 7500 ng/mL (method 2). Good accuracy (bias < -8.6%) and precision (RSD < 8.5%) were obtained for both methods. Thus, they can be employed to analyze coixol in plant extracts and herbal formulations. Copyright © 2017 John Wiley & Sons, Ltd.

  16. Characterization and profiling of phenolic amides from Cortex Lycii by ultra-high performance liquid chromatography coupled with LTQ-Orbitrap mass spectrometry.

    PubMed

    Zhang, Jingxian; Guan, Shuhong; Sun, Jianghao; Liu, Tian; Chen, Pei; Feng, Ruihong; Chen, Xin; Wu, Wanying; Yang, Min; Guo, De-An

    2015-01-01

    Cortex Lycii, the root bark of Lycium chinense Mill. or Lycium barbarum L., is a frequently used traditional Chinese medicine. Phytochemical studies have shown that phenolic amides are not only characteristic compounds but also abundant ones in this plant. In the present study, an effective method was developed for structural characterization of phenolic amides from Cortex Lycii by ultra-high performance liquid chromatography coupled with linear ion trap Orbitrap tandem mass spectrometry. The fragmentation of 14 compounds including six cinnamic acid amides, six neolignanamides, and two lignanamides were studied systematically for the first time. It was found that, in the positive ion mode, neutral loss of the tyramide moiety (137 Da) or N-(4-aminobutyl)acetamide moiety (130 Da) were characteristic for these compounds. At least 54 phenolic amides were detected in the extract and 48 of them were characterized, among which 14 known compounds were identified unambiguously by comparing the retention time and mass spectra with those of reference compounds, and 34 components were tentatively identified based on the fragmentation patterns, exact mass, UV spectra, as well as retention time. Fifteen compounds were characterized as potential new ones. Additionally, the developed method was applied to analyze eight batches of samples collected from the northwest of China, and it was found that cinnamic acid amides were the main type of phenolic amides in Cortex Lycii. In conclusion, the identification of these chemicals provided essential data for further phytochemical studies, metabolites identification, and the quality control of Cortex Lycii.

  17. Rapid and reliable quantitation of amino acids and myo-inositol in mouse brain by high performance liquid chromatography and tandem mass spectrometry.

    PubMed

    Bathena, Sai P; Huang, Jiangeng; Epstein, Adrian A; Gendelman, Howard E; Boska, Michael D; Alnouti, Yazen

    2012-04-15

    Amino acids and myo-inositol have long been proposed as putative biomarkers for neurodegenerative diseases. Accurate measures and stability have precluded their selective use. To this end, a sensitive liquid chromatography tandem mass spectrometry (LC-MS/MS) method based on multiple reaction monitoring was developed to simultaneously quantify glutamine, glutamate, γ-aminobutyric acid (GABA), aspartic acid, N-acetyl aspartic acid, taurine, choline, creatine, phosphocholine and myo-inositol in mouse brain by methanol extractions. Chromatography was performed using a hydrophilic interaction chromatography silica column within in a total run time of 15 min. The validated method is selective, sensitive, accurate, and precise. The method has a limit of quantification ranging from 2.5 to 20 ng/ml for a range of analytes and a dynamic range from 2.5-20 to 500-4000 ng/ml. This LC-MS/MS method was validated for biomarker discovery in models of human neurological disorders. Copyright © 2012 Elsevier B.V. All rights reserved.

  18. Determination of endocrine disrupting chemicals and antiretroviral compounds in surface water: A disposable sorptive sampler with comprehensive gas chromatography - Time-of-flight mass spectrometry and large volume injection with ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Wooding, Madelien; Rohwer, Egmont R; Naudé, Yvette

    2017-05-05

    Many rural dwellers and inhabitants of informal settlements in South Africa are without access to treated water and collect untreated water from rivers and dams for personal use. Endocrine disrupting chemicals (EDCs) have been detected in surface water and wildlife of South Africa. EDCs are often present in complex environmental matrices at ultra-trace levels complicating detection thereof. We report a simplified multi-residue approach for the detection and quantification of EDCs, emerging EDCs, and antiretroviral drugs in surface water. A low cost (less than one US dollar), disposable, sorptive extraction sampler was prepared in-house. The disposable samplers consisted of polydimethylsiloxane (PDMS) tubing fashioned into a loop which was then placed in water samples to concentrate EDCs and emerging pollutants. The PDMS samplers were thermally desorbed directly in the inlet of a GC, thereby eliminating the need for expensive consumable cryogenics. Comprehensive gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS) was used for compound separation and identification. Linear retention indices of EDCs and emerging pollutants were determined on a proprietary Crossbond ® phase Rtx ® -CLPesticides II GC capillary column. In addition, large volume injection of surface water into an ultra-performance liquid chromatograph tandem mass spectrometer (UPLC-MS/MS) was used as complementary methodology for the detection of less volatile compounds. Large volume injection reduced tedious and costly sample preparation steps. Limits of detection for the GC method ranged from 1 to 98pg/l and for the LC method from 2 to 135ng/l. Known and emerging EDCs such as pharmaceuticals, personal care products and pesticides, as well as the antiretroviral compounds, efavirenz and nevirapine, were detected in surface water from South Africa at concentration levels ranging from 0.16ng/l to 227ng/l. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Determination of pharmaceutical and illicit drugs in oral fluid by ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Di Corcia, D; Lisi, S; Pirro, V; Gerace, E; Salomone, A; Vincenti, M

    2013-05-15

    A simple and extremely fast procedure for the quantitative determination in oral fluid samples of 44 substances, including the most common drugs of abuse and several pharmaceutical drugs, was developed and fully validated. Preliminary sample treatment was limited to protein precipitation. The resulting acetonitrile solution was directly injected into an ultra-high performance liquid chromatograph (UHPLC) equipped with a C18 column (100mm×2.1mm, 1.7μm). The mobile phase eluted with linear gradient (water/formic acid 5mM: acetonitrile/formic acid 5mM; v:v) from 98:2 to 0:100 in 5.0min, followed by isocratic elution at 100% B for 1.0min. The flow rate was 0.6mL/min and the total run time was 9.0min including re-equilibration at the initial conditions. The analytes were revealed by a triple quadrupole mass spectrometer operating in the selected reaction monitoring mode. The method proved to be simple, accurate, rapid and highly sensitive, allowing the simultaneous detection of all compounds. The ease of sample treatment, together with the wide range of detectable substances, all with remarkable analytical sensitivity, make this procedure ideal for the screening of large populations in several forensic and clinical contexts, whenever oral fluid sampling has to be preferred to blood sampling, as for example in short retrospective investigations. Copyright © 2013 Elsevier B.V. All rights reserved.

  20. New approach to the determination phosphorothioate oligonucleotides by ultra high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry.

    PubMed

    Studzińska, Sylwia; Mounicou, Sandra; Szpunar, Joanna; Łobiński, Ryszard; Buszewski, Bogusław

    2015-01-15

    This text presents a novel method for the separation and detection of phosphorothioate oligonucleotides with the use of ion pair ultra high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry The research showed that hexafluoroisopropanol/triethylamine based mobile phases may be successfully used when liquid chromatography is coupled with such elemental detection. However, the concentration of both HFIP and TEA influences the final result. The lower concentration of HFIP, the lower the background in ICP-MS and the greater the sensitivity. The method applied for the analysis of serum samples was based on high resolution inductively coupled plasma mass spectrometry. Utilization of this method allows determination of fifty times lower quantity of phosphorothioate oligonucleotides than in the case of quadrupole mass analyzer. Monitoring of (31)P may be used to quantify these compounds at the level of 80 μg L(-1), while simultaneous determination of sulfur is very useful for qualitative analysis. Moreover, the results presented in this paper demonstrate the practical applicability of coupling LC with ICP-MS in determining phosphorothioate oligonucleotides and their metabolites in serum within 7 min with a very good sensitivity. The method was linear in the concentration range between 0.2 and 3 mg L(-1). The limit of detection was in the range of 0.07 and 0.13 mg L(-1). Accuracy varied with concentration, but was in the range of 3%. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Characterization of physalins and fingerprint analysis for the quality evaluation of Physalis alkekengi L. var. franchetii by ultra-performance liquid chromatography combined with diode array detection and electrospray ionization tandem mass spectrometry.

    PubMed

    Zheng, Yunliang; Luan, Lianjun; Chen, Yong; Ren, Yiping; Wu, Yongjiang

    2012-12-01

    Physalins are important bioactive compounds from genus Physalis. They often occur as isomers, which makes the structural elucidation difficult. In the present study, the fragmentation behavior and UV characteristics of seven physalins from genus Physalis were firstly investigated using electrospray ionization tandem mass spectrometry (ESI-MS/MS) and diode array detection (DAD). Combined with ultra-performance liquid chromatography (UPLC) and DAD, the established approach to the structural identification of physalins by ESI-MS/MS was then applied to the analysis of Physalis alkekengi L. According to the UPLC retention behavior, the diagnostic UV spectra and the molecular structural information provided by MS/MS spectra, about 19 fingerprint peaks were identified, including 14 physalins and 5 other compounds. Finally, the established fingerprint method was applied to the analysis of 31 P. alkekengi L. samples collected from different locations, which reflected their similar chemical constituent properties. The proposed method provides a scientific and technical platform to the herbal industry for quality control and safety assurance of herbal preparations that contain this class of physalins. Copyright © 2012 Elsevier B.V. All rights reserved.

  2. Pharmacokinetics and tissue distribution study of schisandrin B in rats by ultra-fast liquid chromatography with tandem mass spectrometry.

    PubMed

    Zhu, Heyun; Zhang, Xiurong; Guan, Jiao; Cui, Baiji; Zhao, Longshan; Zhao, Xu

    2013-05-05

    A rapid, sensitive and high throughput ultra-fast liquid chromatography with tandem mass spectrometry (UFLC-MS/MS) method was established and validated for the determination of schisandrin B in rat plasma and various tissues (including heart, liver, spleen, lung, and kidney). The biological samples were prepared by protein precipitation, and the separation was achieved on a shim-pack XR-ODS C18 column (75 mm × 3.0 mm, 2.2 μm) with a mobile phase consisting of methanol-0.1% formic acid water (85:15, v/v) at a flow rate of 0.4 mL/min. The MS/MS detection was performed on an API 3200 QTRAP mass spectrometry equipped with electrospray ionization (ESI) source using multiple reactions monitoring (MRM) mode by monitoring the fragmentation of m/z 401.2→300.2 for schisandrin B and m/z 271.2→203.1 for imperatorin (internal standard, IS). The calibration curve was linear in the range of 1-500 ng/mL for plasma and tissue homogenates (r ≥ 0.9927). The lower limit of quantification (LLOQ) was 1 ng/mL. The validated method was successfully applied to the pharmacokinetics and tissue distribution study of schisandrin B after oral administration to rats. The pharmacokinetic curve showed double peaks after oral administration, which demonstrated that a hepatoenteral circulation may exist. Tissue distribution showed the highest level was observed in liver, then in kidney, which indicated schisandrin B was mainly accumulated in liver and renal excretion might be a main elimination route. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Ultra Performance Liquid Chromatography with Tandem Mass Spectrometry for the Quantitation of Seventeen Sedative Hypnotics in Six Common Toxicological Matrices.

    PubMed

    Mata, Dani C; Davis, John F; Figueroa, Ariana K; Stanford, Mary June

    2016-01-01

    An ultra performance liquid chromatography triple quadrupole mass spectrometry (LC-MS-MS) method for the quantification of 14 benzodiazepines and three sedative hypnotics is presented. The fast and inexpensive assay was developed for California's Orange County Crime Lab for use in antemortem (AM) and postmortem casework. The drugs were rapidly cleaned up from AM blood, postmortem blood, urine, liver, brain and stomach contents using DPX(®) Weak Anion Exchange (DPX WAX) tips fitted on a pneumatic extractor, which can process up to 48 samples at one time. Assay performance was determined for validation based on recommendations by the Scientific Working Group for Forensic Toxicology for linearity, limit of quantitation, limit of detection, bias, precision (within run and between run), dilution integrity, carry-over, selectivity, recovery, ion suppression and extracted sample stability. Linearity was verified using the therapeutic and toxic ranges of all 17 analytes. Final verification of the method was confirmed by four analysts using 20 blind matrix matched samples. All results were within 20% of each other and the expected value. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  4. The simple determination method for anthocyanidin aglycones in fruits using ultra-high-performance liquid chromatography.

    PubMed

    Shim, You-Shin; Yoon, Won-Jin; Kim, Dong-Man; Watanabe, Masaki; Park, Hyun-Jin; Jang, Hae Won; Lee, Jangho; Ha, Jaeho

    2015-01-01

    The simple determination method for anthocyanidin aglycones in fruits using ultra-high-performance liquid chromatography (UHPLC) coupled with the heating-block acidic hydrolysis method was validated through the precision, accuracy and linearity. The UHPLC separation was performed on a reversed-phase C18 column (particle size 2 μm, i.d. 2 mm, length 100 mm) with a photodiode-array detector. The limits of detection and quantification of the UHPLC analyses were 0.09 and 0.29 mg/kg for delphinidin, 0.08 and 0.24 mg/kg for cyanidin, 0.09 and 0.26 mg/kg for petunidin, 0.14 and 0.42 mg/kg for pelargonidin, 0.16 and 0.48 mg/kg for peonidin and 0.30 and 0.91 mg/kg for malvidin, respectively. The intra- and inter-day precisions of individual anthocyanidin aglycones were <10.3%. All calibration curves exhibited good linearity (r = 0.999) within the tested ranges. The total run time of UHPLC was 8 min. The simple preparation method with UHPLC detection in this study presented herein significantly improved the speed and the simplicity for preparation step of delphinidin, cyanidin, petunidin, pelargonidin, peonidin and malvidin in fruits. Especially, the UHPLC detection exhibited good resolution in spite of shorter run time about four times than conventional HPLC detection. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  5. Determination of dabigatran, rivaroxaban and apixaban by ultra-performance liquid chromatography - tandem mass spectrometry (UPLC-MS/MS) and coagulation assays for therapy monitoring of novel direct oral anticoagulants.

    PubMed

    Schmitz, E M H; Boonen, K; van den Heuvel, D J A; van Dongen, J L J; Schellings, M W M; Emmen, J M A; van der Graaf, F; Brunsveld, L; van de Kerkhof, D

    2014-10-01

    Three novel direct oral anticoagulants (DOACs) have recently been registered by the Food and Drug Administration and European Medicines Agency Commission: dabigatran, rivaroxaban, and apixaban. To quantify DOACs in plasma, various dedicated coagulation assays have been developed. To develop and validate a reference ultra-performance liquid chromatography - tandem mass spectrometry (UPLC-MS/MS) method and to evaluate the analytical performance of several coagulation assays for quantification of dabigatran, rivaroxaban, and apixaban. The developed UPLC-MS/MS method was validated by determination of precision, accuracy, specificity, matrix effects, lower limits of detection, carry-over, recovery, stability, and robustness. The following coagulation assays were evaluated for accuracy and precision: laboratory-developed (LD) diluted thrombin time (dTT), Hemoclot dTT, Pefakit PiCT, ECA, Liquid anti-Xa, Biophen Heparin (LRT), and Biophen DiXal anti-Xa. Agreement between the various coagulation assays and UPLC-MS/MS was determined with random samples from patients using dabigatran or rivaroxaban. The UPLC-MS/MS method was shown to be accurate, precise, sensitive, stable, and robust. The dabigatran coagulation assay showing the best precision, accuracy and agreement with the UPLC-MS/MS method was the LD dTT test. For rivaroxaban, the anti-factor Xa assays were superior to the PiCT-Xa assay with regard to precision, accuracy, and agreement with the reference method. For apixaban, the Liquid anti-Xa assay was superior to the PiCT-Xa assay. Statistically significant differences were observed between the various coagulation assays as compared with the UPLC-MS/MS reference method. It is currently unknown whether these differences are clinically relevant. When DOACs are quantified with coagulation assays, comparison with a reference method as part of proficiency testing is therefore pivotal. © 2014 International Society on Thrombosis and Haemostasis.

  6. Quantitative Analysis of Tetramethylenedisulfotetramine ("Tetramine") Spiked into Beverages by Liquid Chromatography Tandem Mass Spectrometry with Validation by Gas Chromatography Mass Spectrometry

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Owens, J; Hok, S; Alcaraz, A

    Tetramethylenedisulfotetramine, commonly known as tetramine, is a highly neurotoxic rodenticide (human oral LD{sub 50} = 0.1 mg/kg) used in hundreds of deliberate food poisoning events in China. Here we describe a method for quantitation of tetramine spiked into beverages, including milk, juice, tea, cola, and water and cleaned up by C8 solid phase extraction and liquid-liquid extraction. Quantitation by high performance liquid chromatography tandem mass spectrometry (LC/MS/MS) was based upon fragmentation of m/z 347 to m/z 268. The method was validated by gas chromatography mass spectrometry (GC/MS) operated in SIM mode for ions m/z 212, 240, and 360. The limitmore » of quantitation was 0.10 {micro}g/mL by LC/MS/MS versus 0.15 {micro}g/mL for GC/MS. Fortifications of the beverages at 2.5 {micro}g/mL and 0.25 {micro}g/mL were recovered ranging from 73-128% by liquid-liquid extraction for GC/MS analysis, 13-96% by SPE and 10-101% by liquid-liquid extraction for LC/MS/MS analysis.« less

  7. Rapid determination of tafenoquine in small volume human plasma samples by high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Doyle, E; Fowles, S E; Summerfield, S; White, T J

    2002-03-25

    A method was developed for the determination of tafenoquine (I) in human plasma using high-performance liquid chromatography-tandem mass spectrometry. Prior to analysis, the protein in plasma samples was precipitated with methanol containing [2H3(15N)]tafenoquine (II) to act as an internal standard. The supernatant was injected onto a Genesis-C18 column without any further clean-up. The mass spectrometer was operated in the positive ion mode, employing a heat assisted nebulisation, electrospray interface. Ions were detected in multiple reaction monitoring mode. The assay required 50 microl of plasma and was precise and accurate within the range 2 to 500 ng/ml. The average within-run and between-run relative standard deviations were < 7% at 2 ng/ml and greater concentrations. The average accuracy of validation standards was generally within +/- 4% of the nominal concentration. There was no evidence of instability of I in human plasma following three complete freeze-thaw cycles and samples can safely be stored for at least 8 months at approximately -70 degrees C. The method was very robust and has been successfully applied to the analysis of clinical samples from patients and healthy volunteers dosed with I.

  8. Liquid chromatography-mass spectrometry in metabolomics research: mass analyzers in ultra high pressure liquid chromatography coupling.

    PubMed

    Forcisi, Sara; Moritz, Franco; Kanawati, Basem; Tziotis, Dimitrios; Lehmann, Rainer; Schmitt-Kopplin, Philippe

    2013-05-31

    The present review gives an introduction into the concept of metabolomics and provides an overview of the analytical tools applied in non-targeted metabolomics with a focus on liquid chromatography (LC). LC is a powerful analytical tool in the study of complex sample matrices. A further development and configuration employing Ultra-High Pressure Liquid Chromatography (UHPLC) is optimized to provide the largest known liquid chromatographic resolution and peak capacity. Reasonably UHPLC plays an important role in separation and consequent metabolite identification of complex molecular mixtures such as bio-fluids. The most sensitive detectors for these purposes are mass spectrometers. Almost any mass analyzer can be optimized to identify and quantify small pre-defined sets of targets; however, the number of analytes in metabolomics is far greater. Optimized protocols for quantification of large sets of targets may be rendered inapplicable. Results on small target set analyses on different sample matrices are easily comparable with each other. In non-targeted metabolomics there is almost no analytical method which is applicable to all different matrices due to limitations pertaining to mass analyzers and chromatographic tools. The specifications of the most important interfaces and mass analyzers are discussed. We additionally provide an exemplary application in order to demonstrate the level of complexity which remains intractable up to date. The potential of coupling a high field Fourier Transform Ion Cyclotron Resonance Mass Spectrometer (ICR-FT/MS), the mass analyzer with the largest known mass resolving power, to UHPLC is given with an example of one human pre-treated plasma sample. This experimental example illustrates one way of overcoming the necessity of faster scanning rates in the coupling with UHPLC. The experiment enabled the extraction of thousands of features (analytical signals). A small subset of this compositional space could be mapped into a mass

  9. Metabolite characterization of a novel sedative drug, remimazolam in human plasma and urine using ultra high-performance liquid chromatography coupled with synapt high-definition mass spectrometry.

    PubMed

    Zhou, Ying; Hu, Pei; Jiang, Ji

    2017-04-15

    Remimazolam is a new chemical entity belonging to the benzodiazepine class of sedative drugs, which shows faster-acting onset and recovery than currently available short-acting sedatives. In the present study, ultra high performance liquid chromatography with synapt high-definition mass spectrometry method combined with MassLynx software was established to characterize metabolites of remimazolam in human plasma and urine. In total, 5 human metabolites were detected, including 3 phase I and 2 phase II metabolites. There was no novel human metabolite detected compared to that in rat. Hydrolysis, glucuronidation and oxidation were the major metabolic reactions. To our knowledge, this is the first report of the human metabolic profile of remimazolam. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Nonesterified fatty acid determination for functional lipidomics: comprehensive ultrahigh performance liquid chromatography-tandem mass spectrometry quantitation, qualification, and parameter prediction.

    PubMed

    Hellmuth, Christian; Weber, Martina; Koletzko, Berthold; Peissner, Wolfgang

    2012-02-07

    Despite their central importance for lipid metabolism, straightforward quantitative methods for determination of nonesterified fatty acid (NEFA) species are still missing. The protocol presented here provides unbiased quantitation of plasma NEFA species by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Simple deproteination of plasma in organic solvent solution yields high accuracy, including both the unbound and initially protein-bound fractions, while avoiding interferences from hydrolysis of esterified fatty acids from other lipid classes. Sample preparation is fast and nonexpensive, hence well suited for automation and high-throughput applications. Separation of isotopologic NEFA is achieved using ultrahigh-performance liquid chromatography (UPLC) coupled to triple quadrupole LC-MS/MS detection. In combination with automated liquid handling, total assay time per sample is less than 15 min. The analytical spectrum extends beyond readily available NEFA standard compounds by a regression model predicting all the relevant analytical parameters (retention time, ion path settings, and response factor) of NEFA species based on chain length and number of double bonds. Detection of 50 NEFA species and accurate quantification of 36 NEFA species in human plasma is described, the highest numbers ever reported for a LC-MS application. Accuracy and precision are within widely accepted limits. The use of qualifier ions supports unequivocal analyte verification. © 2012 American Chemical Society

  11. Ultra-high performance liquid chromatography with fluorescence detection following salting-out assisted liquid-liquid extraction for the analysis of benzimidazole residues in farm fish samples.

    PubMed

    Tejada-Casado, Carmen; Lara, Francisco J; García-Campaña, Ana M; Del Olmo-Iruela, Monsalud

    2018-03-30

    Ultra-high performance liquid chromatography (UHPLC) coupled with fluorescence detection (FL) has been proposed for the first time to determine thirteen benzimidazoles (BZs) in farmed fish samples. In order to optimize the chromatographic separation, parameters such as mobile phase composition and flow rate were carefully studied, establishing a gradient mode with a mobile phase consisted of water (solvent A) and acetonitrile (solvent B) at a flow rate of 0.4 mL/min. The separation was performed on a Zorbax Eclipse Plus RRHD C 18 column (50 × 2.1 mm, 1.8 μm), involving a total analysis time lower than 12 min. Salting-out assisted liquid-liquid extraction (SALLE) was applied as sample treatment to different types of farmed fish (trout, sea bream and sea bass). To obtain satisfactory extraction efficiencies for the studied analytes, several parameters affecting the SALLE procedure were optimized including the amount of sample, type and volume of the extraction solvent, and the nature and amount of the salt used. Characterization of the method in terms of performance characteristics was carried out, obtaining satisfactory results for the linearity (R 2  ≥ 0.997), repeatability (RSD ≤ 6.1%), reproducibility (RSD ≤ 10.8%) and recoveries (R ≥ 79%; RSD ≤ 7.8%). Detection limits between 0.04-29.9 μg kg -1 were obtained, demonstrating the applicability of this fast, simple and environmentally friendly method. Copyright © 2018 Elsevier B.V. All rights reserved.

  12. Screening bioactive quality control markers of QiShenYiQi dripping pills based on the relationship between the ultra-high performance liquid chromatography fingerprint and vascular protective activity.

    PubMed

    Zhuo, Limeng; Peng, Jingjing; Zhao, Yunli; Li, Dongxiang; Xie, Xiuman; Tong, Ling; Yu, Zhiguo

    2017-10-01

    Traditional Chinese medicine consists of complex phytochemical constituents. Selecting appropriate analytical markers of traditional Chinese medicine is a critical step in quality control. Currently, the combination of fingerprinting and efficacy evaluation is considered as a useful method for screening active ingredients in complex mixtures. This study was designed to develop an orthogonal partial least squares model for screening bioactive quality control markers of QishenYiqi dripping pills based on the fingerprint-efficacy relationship. First, the chemical fingerprints of 49 batches of QishenYiqi dripping pill samples were established by ultra-high performance liquid chromatography coupled with a photodiode array detector. Second, ultra-high performance liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry was exploited to systematically investigate the 36 copossessing fingerprint components in QishenYiqi dripping pills. The vascular protective activity of QishenYiqi dripping pills was determined by using a cell counting kit-8 assay. Finally, fingerprint-efficacy relationship was established by orthogonal partial least squares model. The results indicated that ten components exhibited strong correlation with vascular protective activity, and these were preliminarily screened as quality control markers. The present study provided a novel idea for the study of the pharmacodynamic material basis and quality evaluation of QishenYiqi dripping pills. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Detection of anabolic and androgenic steroids and/or their esters in horse hair using ultra-high performance liquid chromatography-high resolution mass spectrometry.

    PubMed

    Kwok, Karen Y; Choi, Timmy L S; Kwok, Wai Him; Wong, Jenny K Y; Wan, Terence S M

    2017-04-14

    Anabolic and androgenic steroids (AASs) are a class of prohibited substances banned in horseracing at all times. The common approach for controlling the misuse of AASs in equine sports is by detecting the presence of AASs and/or their metabolites in urine and blood samples using gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). This approach, however, often falls short as the duration of effect for many AASs are longer than their detection time in both urine and blood. As a result, there is a high risk that such AASs could escape detection in their official race-day samples although they may have been used during the long period of training. Hair analysis, on the other hand, can afford significantly longer detection windows. In addition, the identification of synthetic ester derivatives of AASs in hair, particularly for the endogenous ones, can provide unequivocal proof of their exogenous origin. This paper describes the development of a sensitive method (at sub to low parts-per-billion or ppb levels) for detecting 48 AASs and/or their esters in horse hair using ultra-high performance liquid chromatography-high resolution mass spectrometry (UHPLC-HRMS). Decontaminated horse hair was pulverised and subjected to in-situ liquid-liquid extraction in a mixture of hexane - ethyl acetate (7:3, v/v) and phosphate buffer (0.1M, pH 9.5), followed by additional clean-up using mixed-mode solid-phase extraction. The final extract was analysed using UHPLC-HRMS in the positive electrospray ionisation (ESI) mode with both full scan and parallel reaction monitoring (PRM). This method was validated for qualitative identification purposes. Validation data, including method specificity, method sensitivity, extraction recovery, method precision and matrix effect are presented. Method applicability was demonstrated by the successful detection and confirmation of testosterone propionate in a referee hair sample. To our knowledge, this was

  14. Determination of geniposide in adjuvant arthritis rat plasma by ultra-high performance liquid chromatography tandem mass spectrometry method and its application to oral bioavailability and plasma protein binding ability studies.

    PubMed

    Chen, Jian; Wu, Hong; Xu, Guo-Bing; Dai, Miao-Miao; Hu, Shun-Li; Sun, Liang-Liang; Wang, Wei; Wang, Rong; Li, Shu-Pin; Li, Guo-Qiang

    2015-04-10

    A specific, sensitive and high throughput ultra-high performance liquid chromatography-electrospray ionization tandem mass spectrometric method (UHPLC-ESI-MS/MS) was established and validated to assay geniposide (GE), a promising anti-inflammatory drug, in adjuvant arthritis rat plasma: application to pharmacokinetic and oral bioavailability studies and plasma protein binding ability. Plasma samples were processed by de-proteinised with ice-cold methanol and separated on an ACQUITY UPLC™ HSS C18 column (100 mm × 2.1mm i.d., 1.8 μm particle size) at a gradient flow rate of 0.2 mL/min using acetonitrile-0.1% formic acid in water as mobile phase, and the total run time was 9 min. Mass detection was performed in selected reaction monitoring (SRM) mode with negative electro-spray ionization includes the addition of paeoniflorin (Pae) as an internal standard (IS). The mass transition ion-pair was followed as m/z 387.4 → 122.4 for GE and m/z 479.4 → 449.0 for IS. The calibration curves were linear over the concentration range of 2-50,000 ng/mL with lower limit of quantification of 2 ng/mL. The intra-day and inter-day precisions (RSD, %) of the assay were less than 8.4%, and the accuracy was within ± 6.4% in terms of relative error (RE). Extraction recovery, matrix effect and stability were satisfactory in adjuvant arthritis rat plasma. The UHPLC-ESI-MS/MS method was successfully applied to a pharmacokinetic study of GE after oral administration of depurated GE at 33, 66, 132 mg/kg and intravenous injection at 33, 66, 132 mg/kg in adjuvant arthritis (AA) rats. In addition, it was found that GE has rapid absorption and elimination, low absolute bioavailability, high plasma protein binding ability in AA rats after oral administration within the tested dosage range. It suggested that GE showed slow distribution into the intra- and extracellular space, and the binding rate was not proportionally dependent on plasma concentration of GE when the concentration of GE was

  15. Determination of mycotoxins in plant-based beverages using QuEChERS and liquid chromatography-tandem mass spectrometry.

    PubMed

    Miró-Abella, Eugènia; Herrero, Pol; Canela, Núria; Arola, Lluís; Borrull, Francesc; Ras, Rosa; Fontanals, Núria

    2017-08-15

    A method was developed for the simultaneous determination of 11 mycotoxins in plant-based beverage matrices, using a QuEChERS extraction followed by ultra-high performance liquid chromatography coupled to tandem mass spectrometry detection (UHPLC-(ESI)MS/MS). This multi-mycotoxin method was applied to analyse plant-based beverages such as soy, oat and rice. QuEChERS extraction was applied obtaining suitable extraction recoveries between 80 and 91%, and good repeatability and reproducibility values. Method Quantification Limits were between 0.05μgL -1 (for aflatoxin G 1 and aflatoxin B 1 ) and 15μgL -1 (for deoxynivalenol and fumonisin B 2 ). This is the first time that plant-based beverages have been analysed, and certain mycotoxins, such as deoxynivalenol, aflatoxin B 1 , aflatoxin B 2 , aflatoxin G 1 , aflatoxin G 2 , ochratoxin A, T-2 toxin and zearalenone, were found in the analysed samples, and some of them quantified between 0.1μgL -1 and 19μgL -1 . Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Ultra-fast liquid chromatography with tandem mass spectrometry determination of eight bioactive components of Kai-Xin-San in rat plasma and its application to a comparative pharmacokinetic study in normal and Alzheimer's disease rats.

    PubMed

    Wang, Xiaotong; Zhang, Yue; Niu, Huibin; Geng, Yajing; Wang, Bing; Yang, Xiaomei; Yan, Pengyu; Li, Qing; Bi, Kaishun

    2017-05-01

    A method of ultra-fast liquid chromatography with tandem mass spectrometry was developed and validated for the simultaneous quantitation of eight bioactive components, including polygalaxanthone III, sibiricaxanthone B, tenuifolin, sibiricose A5, sibiricose A6, tenuifoliside A, ginsenoside Re and ginsenoside Rb1 in rat plasma after oral administration of Kai-Xin-San. The plasma samples were extracted by liquid-liquid extraction using digoxin as an internal standard. Chromatographic separation was performed on a Venusil MP C 18 column (100 mm × 2.1 mm, 3 μm) with methanol and 0.05% acetic acid in water as mobile phase. The tandem mass spectrometric detection was performed in the multiple reaction monitoring with turbo ion spray source in the negative ionization. Validation parameters were within acceptable ranges. The established method has been successfully applied to compare the pharmacokinetic profiles of the analytes between normal and Alzheimer's disease rats. The results indicated that there were significant differences in pharmacokinetic parameters of some components between two groups, which may be due to the mechanisms of Alzheimer's disease and pharmacological effects of the analytes. The pharmacokinetic research in the pathological state might provide more useful information to guide the clinical usage of herbal medicine. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Comparison of high-performance liquid chromatography/tandem mass spectrometry and high-performance liquid chromatography/photo-diode array detection for the quantitation of carotenoids, retinyl esters, α-tocopherol and phylloquinone in chylomicron-rich fractions of human plasma.

    PubMed

    Kopec, Rachel E; Schweiggert, Ralf M; Riedl, Ken M; Carle, Reinhold; Schwartz, Steven J

    2013-06-30

    Bioavailability of essential lipophilic micronutrients and carotenoids is of utmost interest for human health, as the consumption of these compounds may help alleviate major nutritional deficiencies, cardiovascular disease, and cancer. High-performance liquid chromatography/photo-diode array detection (HPLC-PDA) and high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) were compared for the quantitative analysis of α- and β-carotene, β-cryptoxanthin, lutein, lycopene, α-tocopherol, phylloquinone, and several retinyl esters from chylomicron-containing triglyceride rich lipoprotein (TRL) fractions of human plasma obtained from two clinical trials. After selecting an efficient extraction method for the analytes, both the HPLC/PDA and the HPLC/MS/MS methods were developed and several parameters validated using an HP 1200 series HPLC system interfaced with a HP 1200 series diode-array detector (Agilent Technologies, Santa Clara, CA, USA) and a QTRAP 5500 (AB Sciex, Foster City, CA, USA) via an atmospheric pressure chemical ionization (APCI) probe operated in positive ion mode. For lycopene, α- and β-carotene, HPLC/MS/MS was up to 37 times more sensitive than HPLC-PDA. PDA detection was shown to be up to 8 times more sensitive for lutein. MS/MS signals were enhanced by matrix components for lutein and β-cryptoxanthin, as determined by referencing to the matrix-independent PDA signal. In contrast, matrix suppression was observed for retinyl palmitate, α-carotene, and β-carotene. Both detectors showed similar suitability for α-tocopherol, lycopene and retinyl palmitate (representing ~73% of total retinyl esters). MS/MS exclusively allowed the quantitation of minor retinyl esters, phylloquinone, and (Z)-lycopene isomers. HPLC/MS/MS was more sensitive than HPLC-PDA for six of the eight analytes and represents a powerful tool for the analysis of chylomicron samples and potentially other biological samples of limited sample size. When internal

  18. Comparison of high-performance liquid chromatography/tandem mass spectrometry and high-performance liquid chromatography/photo-diode array detection for the quantitation of carotenoids, retinyl esters, α-tocopherol and phylloquinone in chylomicron-rich fractions of human plasma

    PubMed Central

    Kopec, Rachel E.; Schweiggert, Ralf M.; Riedl, Ken M.; Carle, Reinhold; Schwartz, Steven J.

    2013-01-01

    Rationale Bioavailability of essential lipophilic micronutrients and carotenoids is of utmost interest for human health, as the consumption of these compounds may help alleviate major nutritional deficiencies, cardiovascular disease, and cancer. High-performance liquid chromatography/photo-diode array detection (HPLC-PDA) and high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) were compared for the quantitative analysis of α- and β-carotene, β-cryptoxanthin, lutein, lycopene, α-tocopherol, phylloquinone, and several retinyl esters from chylomicron-containing triglyceride rich lipoprotein (TRL) fractions of human plasma obtained from two clinical trials. Methods After selecting an efficient extraction method for the analytes, both the HPLC/PDA and the HPLC/MS/MS methods were developed and several parameters validated using an HP 1200 series HPLC system interfaced with a HP 1200 series diode-array detector (Agilent Technologies, Santa Clara, CA, USA) and a QTRAP 5500 (AB Sciex, Foster City, CA, USA) via an atmospheric pressure chemical ionization (APCI) probe operated in positive ion mode. Results For lycopene, α- and β-carotene, HPLC/MS/MS was up to 37 times more sensitive than HPLC-PDA. PDA detection was shown to be up to 8 times more sensitive for lutein. MS/MS signals were enhanced by matrix components for lutein and β-cryptoxanthin, as determined by referencing to the matrix-independent PDA signal. In contrast, matrix suppression was observed for retinyl palmitate, α-carotene, and β-carotene. Both detectors showed similar suitability for α-tocopherol, lycopene and retinyl palmitate (representing ~73% of total retinyl esters). MS/MS exclusively allowed the quantitation of minor retinyl esters, phylloquinone, and (Z)-lycopene isomers. Conclusions HPLC/MS/MS was more sensitive than HPLC-PDA for six of the eight analytes and represents a powerful tool for the analysis of chylomicron samples and potentially other biological samples

  19. Recent advances in micro-scale and nano-scale high-performance liquid-phase chromatography for proteome research.

    PubMed

    Tao, Dingyin; Zhang, Lihua; Shan, Yichu; Liang, Zhen; Zhang, Yukui

    2011-01-01

    High-performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-ESI-MS-MS) is regarded as one of the most powerful techniques for separation and identification of proteins. Recently, much effort has been made to improve the separation capacity, detection sensitivity, and analysis throughput of micro- and nano-HPLC, by increasing column length, reducing column internal diameter, and using integrated techniques. Development of HPLC columns has also been rapid, as a result of the use of submicrometer packing materials and monolithic columns. All these innovations result in clearly improved performance of micro- and nano-HPLC for proteome research.

  20. A rapid method for the simultaneous determination of 25 anti-hypertensive compounds in dietary supplements using ultra-high-pressure liquid chromatography.

    PubMed

    Heo, Seok; Yoo, Geum Joo; Choi, Ji Yeon; Park, Hyoung Joon; Park, Sung-Kwan; Baek, Sun Young

    2016-11-01

    A novel, stable, simple and specific ultra-performance liquid chromatography method with ultraviolet detection (205 nm) for the simultaneous analysis of 25 anti-hypertensive substances was developed. The method was validated according to the International Conference of Harmonisation guidelines with respect to linearity, accuracy, precision, limit of detection (LOD), limit of quantitation (LOQ) and stability. From the ultra-performance liquid chromatography results, we identified the LOD and LOQ of solid samples to be 0.20-1.00 and 0.60-3.00 μg ml -1 , respectively, while those of liquid samples were 0.30-1.20 and 0.90-3.60 μg ml -1 , respectively. The linearity exceeded 0.9999, and the intra- and inter-day precisions were 0.15-6.48% and 0.28-8.67%, respectively. The intra- and inter-day accuracies were 82.25-111.42% and 80.70-115.64%, respectively, and the stability was lower than 12.9% (relative standard deviation). This method was applied to the monitoring of 97 commercially available dietary supplements obtained in Korea, such as pills, soft capsules, hard capsules, liquids, powders and tablets. The proposed method is accurate, precise and of high quality, and can be used for the routine, reproducible analysis and control of 25 anti-hypertensive substances in various dietary supplements. The work presented herein may help to prevent incidents related to food adulteration and restrict the illegal food market.

  1. Observation of T-2 and HT-2 glucosides from Fusarium sporotrichioides by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS)

    USDA-ARS?s Scientific Manuscript database

    Cultures of Fusarium sporotrichioides were extracted and subjected to evaluation by high performance liquid chromatographytandem mass spectrometry (LC-MS/MS). Along with the expected T-2 and HT-2 toxins, compounds 162 m/z higher than the toxins were observed. Fragmentation behavior of the larger ...

  2. Simultaneous analysis of gemfibrozil, morphine, and its two active metabolites in different mouse brain structures using solid-phase extraction with ultra-high performance liquid chromatography and tandem mass spectrometry with a deuterated internal standard.

    PubMed

    Yang, Zizhao; Wang, Lu; Xu, Mingcheng; Gu, Jingkai; Yu, Lushan; Zeng, Su

    2016-06-01

    A rapid and sensitive bioassay was established and validated to simultaneously determine gemfibrozil, morphine, morphine-3β-glucuronide, and morphine-6β-glucuronide in mouse cerebrum, epencephalon, and hippocampus based on ultra-high performance liquid chromatography and tandem mass spectrometry. The deuterated internal standard, M6G-d3, was mixed with the prepared samples at 10 ng/mL as the final concentration. The samples were transferred into the C18 solid-phase extraction columns with gradient elution for solid-phase extraction. The mobile phase consisted of methanol and 0.05% formic acid (pH 3.2). Multiple reaction monitoring has been applied to analyze gemfibrozil (m/z 249.0 → 121.0) in anion mode, and M6G-d3 (m/z 465.1 → 289.1), morphine (m/z 286.0 → 200.9), and M3G and M6G (m/z 462.1 → 286.1) in the positive ion mode. The method has a linear calibration range from 0.05 to 10 ng for gemfibrozil, morphine, and M3G and M6G with correlation coefficients >0.993. The lower limit of quantitation for all four analytes was 0.05 ng/mL, relative standard deviation of intra- and interday precision was less than 10.5%, and the relative error of accuracy was from -8.2 to 8.3% at low, medium, and high concentrations for all the analytes. In conclusion, gemfibrozil can influence the morphine antinociception after coronary heart disease induced chronic angina by the change in one of morphine metabolites', M3G, distribution in mouse brain. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Rapid determination of the various native forms of vitamin B6 and B2 in cow's milk using ultra-high performance liquid chromatography.

    PubMed

    Schmidt, A; Schreiner, M G; Mayer, H K

    2017-06-02

    As the formation of pyridoxal phosphate, the active cofactor of vitamin B 6 , is dependent on riboflavin 5-phosphate, we propose a fast and simple ultra-high performance liquid chromatography method for the simultaneous determination of the native B 6 vitamers pyridoxal, pyridoxine, pyridoxamine, their mono phosphorus esters and 4-pyridoxic acid as well as vitamin B 2 as riboflavin and its phosphorus ester riboflavin 5-phosphate in milk. Separation was achieved under 6.0min by reversed-phase and pH gradient elution. Sample preparation was optimized regarding various acids and pH levels. Changes in those parameters led to significant deviations of sample matrix breakdown efficiency. The optimized method was then validated regarding specificity, accuracy, precision, linearity, range, detection and quantification limits. As the method performed satisfactory, is was used to study commercial liquid cow's milk (n=31), regarding effects of the employed preservation technique (pasteurization, extended shelf-life, ultra-high temperature) on the composition and content of B 6 and B 2 vitamers. In cow's milk, vitamin B 6 mostly consists of pyridoxal and its phosphate ester, with pyridoxal phosphate being the bulk component. The catabolite of the vitamin B 6 metabolism, 4-pyridoxic acid was present in significant amounts in all studied samples, with up to 2.69μmolL -1 . Vitamin B 2 was present as riboflavin and its phosphate ester up to 12.86μmolL -1 . Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Development of a high-throughput method for the determination of ethosuximide in human plasma by liquid chromatography mass spectrometry.

    PubMed

    Bhatt, Mitesh; Shah, Sanjay; Shivprakash

    2010-06-01

    A simple, rapid, sensitive and specific ultra performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method was developed and validated for the quantification of ethosuximide in human plasma is described. Analyte was chromatographed on a Hypersil Gold C18 column (100 mm x 2.1 mm, i.d., 1.9 microm) with isocratic elution at a flow rate of 0.250 mL/min and pravastatin was used as the internal standard. The assay involves a simple solid-phase extraction procedure of 0.25 mL human plasma and the analysis was performed on a triple-quadrupole tandem mass spectrometer by MRM mode via electrospray ionization (ESI). The method was linear in the concentration range of 0.25-60.0 microg/mL. The lower limit of quantification (LLOQ) was 0.25 microg/mL. The within- and between-day precision and accuracy of the quality control samples were within 10.0%. The recovery was 95.1% and 94.4% for ethosuximide and pravastatin, respectively. The analysis time for each sample was 1.8 min. The method was highly reproducible and gave peaks with excellent chromatography properties. Copyright 2010 Elsevier B.V. All rights reserved.

  5. Residue level and dissipation pattern of lepimectin in shallots using high-performance liquid chromatography coupled with photodiode array detection.

    PubMed

    Kim, Sung-Woo; Rahman, Md Musfiqur; Abd El-Aty, A M; Truong, Lieu T B; Choi, Jeong-Heui; Park, Joon-Seong; Kim, Mi-Ra; Shin, Ho-Chul; Shim, Jae-Han

    2016-11-01

    Lepimectin, as an emulsifiable concentrate, was sprayed on shallots at the recommended dose rate (10 mL/20 L) to determine its residue levels, dissipation pattern, pre-harvest residue limits (PHRLs), and health risk. Samples were randomly collected over 10 days, extracted with acetonitrile, purified using an amino solid-phase extraction (NH 2 -SPE) cartridge and analyzed using a high-performance liquid chromatography-photodiode array detection method. Field-incurred samples were confirmed using ultra-performance liquid chromatography-tandem mass spectrometry. The linearity was excellent, with a determination coefficient (R 2 ) of ≥0.9991. The recoveries at two spiking levels (0.2 and 1.0 mg/kg) ranged from 84.49 to 87.64% with relative standard deviations of ≤7.04%. The developed method was applied to field samples grown in separate greenhouses, one located in Naju and one in Muan, in the Republic of Korea. The dissipation pattern was described by first-order kinetics with half-lives of 1.9 (Naju) and 1.7 days (Muan). The PHRL curves indicated that, if the lepimectin residues are <0.18 (Naju) and <0.13 mg/kg (Muan) 5 days before harvest, the residue levels will be lower than the maximum residue limit (0.05 mg/kg) upon harvesting. The risk assessment data indicated that lepimectin is safe for use in the cultivation of shallots, with no risk of detrimental effects to the consumer. Copyright © 2016 John Wiley & Sons, Ltd.

  6. Mallow carotenoids determined by high-performance liquid chromatography

    USDA-ARS?s Scientific Manuscript database

    Mallow (corchorus olitorius) is a green vegetable, which is widely consumed either fresh or dry by Middle East population. This study was carried out to determine the contents of major carotenoids quantitatively in mallow, by using a High Performance Liquid Chromatography (HPLC) equipped with a Bis...

  7. Simple determination of aflatoxins in rice by ultra-high performance liquid chromatography coupled to chemical post-column derivatization and fluorescence detection.

    PubMed

    Huertas-Pérez, José Fernando; Arroyo-Manzanares, Natalia; Hitzler, Dominik; Castro-Guerrero, Francisco Germán; Gámiz-Gracia, Laura; García-Campaña, Ana M

    2018-04-15

    A fast and simple analytical method was developed and characterized for the determination of aflatoxins (B 1 , B 2 , G 1 and G 2 ) in rice. The procedure is based on a simple solid-liquid extraction without further clean-up, and analysis by ultra-high performance liquid chromatography coupled with fluorescence detection. Fluorescence emission of aflatoxins B 1 and G 1 was enhanced by post-column chemical derivatization using pyridinium bromide perbromide. The analytical method was satisfactorily characterized in white and brown rice. Under optimum conditions, external calibration in solvent could be used for quantification purposes and limits of quantification were below the maximum contents established by the European Union regulation for these contaminants/commodity group combination (0.07-0.14 µg/kg for white rice and 0.20-0.28 µg/kg for brown rice). Recovery studies carried out at three different concentration levels (0.5, 2 and 5 µg/kg) showed values in the range of 84.5-105.3%, and RSDs ≤ 5%. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. A strategy for identification and structural characterization of compounds from Gardenia jasminoides by integrating macroporous resin column chromatography and liquid chromatography-tandem mass spectrometry combined with ion-mobility spectrometry.

    PubMed

    Wang, Lu; Liu, Shu; Zhang, Xueju; Xing, Junpeng; Liu, Zhiqiang; Song, Fengrui

    2016-06-24

    In this paper, an analysis strategy integrating macroporous resin (AB-8) column chromatography and high performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) combined with ion mobility spectrometry (IMS) was proposed and applied for identification and structural characterization of compounds from the fruits of Gardenia jasminoides. The extracts of G. jasminoides were separated by AB-8 resin column chromatography combined with reversed phase liquid chromatography (C18 column) and detected by electrospray ionization tandem mass spectrometry. Additionally, ion mobility spectrometry (IMS) was employed as a supplementary separation technique to discover previously undetected isomers from the fruits of G. jasminoides. A total of 71 compounds, including iridoids, flavonoids, triterpenes, monoterpenoids, carotenoids and phenolic acids were identified by the characteristic high resolution mass spectrometry and the ESI-MS/MS fragmentations. In conclusion, the IMS-MS technique achieved the separation of isomers in crocin-3 and crocin-4 according to their acquired mobility drift times differing from classical analysis by mass spectrometry. The proposed strategy can be used as a highly sensitive and efficient procedure for identification and separation isomeric components in extracts of herbal medicines. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Multiresidue analysis of oestrogenic compounds in cow, goat, sheep and human milk using core-shell polydopamine coated magnetic nanoparticles as extraction sorbent in micro-dispersive solid-phase extraction followed by ultra-high-performance liquid chromatography tandem mass spectrometry.

    PubMed

    Socas-Rodríguez, Bárbara; Hernández-Borges, Javier; Herrera-Herrera, Antonio V; Rodríguez-Delgado, Miguel Ángel

    2018-03-01

    In this work, the suitability of Fe 3 O 4 nanoparticles coated with polydopamine was evaluated as sorbent for the extraction of a group of 21 compounds with oestrogenic activity including seven phytoestrogens, six mycotoxins as well as four synthetic and four natural oestrogens from different types of milk, including sheep milk, in which the evaluation of oestrogenic compounds have never been developed before. Extraction was carried out using magnetic micro-dispersive solid-phase extraction after a previous deproteinisation step. Separation, determination and quantification of the target analytes were achieved by ultra-high-performance liquid chromatography coupled to triple quadrupole-tandem mass spectrometry. The methodology was validated for five milk samples using 17β-estradiol-2,4,16,16,17-d 5 as internal standard for natural and synthetic oestrogens, β-zearalanol-10,10,11,12,12-d 5 for mycotoxins and prunetin for phytoestrogens. Recovery values ranged from 70 to 120% for the five types of matrices with relative standard deviation values lower than 18%. Limits of quantification of the method were in the range 0.55-11.8 μg L -1 for all samples. Graphical abstract General scheme of the multiresidue analysis of oestrogenic compounds in milk using core-shell polydopamine coated magnetic nanoparticles as extraction sorbent in μ-dSPE.

  10. Ruggedness testing and validation of a practical analytical method for > 100 veterinary drug residues in bovine muscle by ultrahigh performance liquid chromatographytandem mass spectrometry

    USDA-ARS?s Scientific Manuscript database

    In this study, optimization, extension, and validation of a streamlined, qualitative and quantitative multiclass, multiresidue method was conducted to monitor great than100 veterinary drug residues in meat using ultrahigh-performance liquid chromatographytandem mass spectrometry (UHPLC-MS/MS). I...

  11. Residue analysis of sixty pesticides in red swamp crayfish using QuEChERS with high-performance liquid chromatography-tandem mass spectrometry

    USDA-ARS?s Scientific Manuscript database

    In this study, a multi-residue analytical method using QuEChERS extraction and dispersive solid-phase extraction (d-SPE) cleanup followed by high-performance liquid chromatography–tandem mass spectrometry (HPLC-MS/MS) was developed for rapid determination of 60 pesticide residues in whole crayfish a...

  12. Rapid Characterization and Identification of Flavonoids in Radix Astragali by Ultra-High-Pressure Liquid Chromatography Coupled with Linear Ion Trap-Orbitrap Mass Spectrometry.

    PubMed

    Zhang, Jing; Xu, Xiao-Jie; Xu, Wen; Huang, Juan; Zhu, Da-yuan; Qiu, Xiao-Hui

    2015-07-01

    A simple and effective method was established for separation and characterization of flavonoid constituents in Radix Astragali (RA) by combination of ultra-high-pressure liquid chromatography with LTQ-Orbitrap tandem mass spectrometry (u-HPLC-LTQ-Orbitrap-MS(n)). For three major structural types of flavonoids, the proposed fragmentation pathways and major diagnostic fragment ions of isoflavones, pterocarpans and isoflavans were investigated to trace isoflavonoid derivatives in crude plant extracts. Based on the systematic identification strategy, 48 constituents were rapidly detected and characterized or tentatively identified, many of which were first reported in RA. The u-PHLC-LTQ-Orbitrap MS(n) platform was proved as an effective tool for rapid qualitative analysis of secondary metabolite productions from natural resources. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  13. Quantitation of amyloid beta peptides Aβ(1-38), Aβ(1-40), and Aβ(1-42) in human cerebrospinal fluid by ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Lame, Mary E; Chambers, Erin E; Blatnik, Matthew

    2011-12-15

    Critical events in Alzheimer's disease (AD) involve an imbalance between the production and clearance of amyloid beta (Aβ) peptides from the brain. Current methods for Aβ quantitation rely heavily on immuno-based techniques. However, these assays require highly specific antibodies and reagents that are time-consuming and expensive to develop. Immuno-based assays are also characterized by poor dynamic ranges, cross-reactivity, matrix interferences, and dilution linearity problems. In particular, noncommercial immunoassays are especially subject to high intra- and interassay variability because they are not subject to more stringent manufacturing controls. Combinations of these factors make immunoassays more labor-intensive and often challenging to validate in support of clinical studies. Here we describe a mixed-mode solid-phase extraction method and an ultra-performance liquid chromatography tandem mass spectrometry (SPE UPLC-MS/MS) assay for the simultaneous quantitation of Aβ(1-38), Aβ(1-40), and Aβ(1-42) from human cerebrospinal fluid (CSF). Negative ion versus positive ion species were compared using their corresponding multiple reaction monitoring (MRM) transitions, and negative ions were approximately 1.6-fold greater in intensity but lacked selectivity in matrix. The positive ion MRM assay was more than sufficient to quantify endogenous Aβ peptides. Aβ standards were prepared in artificial CSF containing 5% rat plasma, and quality control samples were prepared in three pooled CSF sources. Extraction efficiency was greater than 80% for all three peptides, and the coefficient of variation during analysis was less than 15% for all species. Mean basal levels of Aβ species from three CSF pools were 1.64, 2.17, and 1.26 ng/ml for Aβ(1-38); 3.24, 3.63, and 2.55 ng/ml for Aβ(1-40); and 0.50, 0.63, and 0.46 ng/ml for Aβ(1-42). Copyright © 2011 Elsevier Inc. All rights reserved.

  14. Improvement and validation of a high-performance liquid chromatography in tandem mass spectrometry method for monitoring of omeprazole in plasma.

    PubMed

    Wojnicz, Aneta; Gil García, Ana Isabel; Román-Martínez, Manuel; Ochoa-Mazarro, Dolores; Abad-Santos, Francisco; Ruiz-Nuño, Ana

    2015-06-01

    Omeprazole (OME) is a proton pump inhibitor with a 58% bioavailability after a single oral dose. It is subject to marked interindividual variations and significant drug-drug interactions. The authors developed a simple and rapid method based on liquid chromatography in tandem with mass spectrometry with solid phase extraction and isotope-labeled internal standard to monitor plasma levels of OME in pharmacokinetics and drug-drug interaction studies. OME and its internal standard (OME-D3) were eluted with a Zorbax Extend C-18 rapid resolution column (4.6 × 50 mm, 3.5 μm) at 25°C, under isocratic conditions through a mobile phase consisting of 1 mM ammonium acetate, pH 8.5 (55%), and acetonitrile (45%). The flow rate was 0.8 mL/min, and the chromatogram run time was 1.2 minutes. OME was detected and quantified by liquid chromatography in tandem with mass spectrometry with positive electrospray ionization, which operates in multiple-reaction monitoring mode. The method was linear in the range of 1.5-2000 ng/mL for OME. The validation assays for accuracy and precision, matrix effect, extraction recovery, and stability of the samples for OME did not deviate more than 20% for the lower limit of quantification and no more than 15% for other quality controls. These findings are consistent with the requirements of regulatory agencies. The method enables rapid quantification of OME concentrations and can be used in pharmacokinetic and drug-drug interaction studies.

  15. Chemical Profiling of Re-Du-Ning Injection by Ultra-Performance Liquid Chromatography Coupled with Electrospray Ionization Tandem Quadrupole Time-of-Flight Mass Spectrometry through the Screening of Diagnostic Ions in MSE Mode

    PubMed Central

    Wang, Zhenzhong; Geng, Jianliang; Dai, Yi; Xiao, Wei; Yao, Xinsheng

    2015-01-01

    The broad applications and mechanism explorations of traditional Chinese medicine prescriptions (TCMPs) require a clear understanding of TCMP chemical constituents. In the present study, we describe an efficient and universally applicable analytical approach based on ultra-performance liquid chromatography coupled to electrospray ionization tandem quadrupole time-of-flight mass spectrometry (UPLC-ESI-Q/TOF-MS) with the MSE (E denotes collision energy) data acquisition mode, which allowed the rapid separation and reliable determination of TCMP chemical constituents. By monitoring diagnostic ions in the high energy function of MSE, target peaks of analogous compounds in TCMPs could be rapidly screened and identified. “Re-Du-Ning” injection (RDN), a eutherapeutic traditional Chinese medicine injection (TCMI) that has been widely used to reduce fever caused by viral infections in clinical practice, was studied as an example. In total, 90 compounds, including five new iridoids and one new sesquiterpene, were identified or tentatively characterized by accurate mass measurements within 5 ppm error. This analysis was accompanied by MS fragmentation and reference standard comparison analyses. Furthermore, the herbal sources of these compounds were unambiguously confirmed by comparing the extracted ion chromatograms (EICs) of RDN and ingredient herbal extracts. Our work provides a certain foundation for further studies of RDN. Moreover, the analytical approach developed herein has proven to be generally applicable for profiling the chemical constituents in TCMPs and other complicated mixtures. PMID:25875968

  16. Metabolomic approaches for orange origin discrimination by ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry.

    PubMed

    Díaz, Ramon; Pozo, Oscar J; Sancho, Juan V; Hernández, Félix

    2014-08-15

    In this work, hybrid quadrupole time-of-flight mass spectrometer (QTOF MS) coupled to ultra high performance liquid chromatography (UHPLC) has been used for biomarkers identification for correct authentication of Valencia (Spain) oranges. Differentiation from foreign Argentinean, Brazilian and South African oranges has been carried out using XCMS application and multivariate analysis to UHPLC-(Q)TOF MS data acquired in both, positive and negative ionisation modes. Several markers have been found and corroborated by analysing two seasons samples. A seasonal independent marker was found and its structure elucidated using accurate mass data and MS(E) fragmentation spectrum information. Empirical formula was searched in Reaxys database applying sub-structure filtering from the fragments obtained. Three possible structures were found and citrusin D, a compound present in sweet oranges, has been identified as the most plausible as it fits better with the product ion scan performed for this compound. As a result of data obtained in this work, citrusin D is suggested as a potential marker to distinguish the geographic origin of oranges. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Ultra-pressure liquid chromatography/tandem mass spectrometry targeted profiling of arachidonic acid and eicosanoids in human colorectal cancer.

    PubMed

    Mal, Mainak; Koh, Poh Koon; Cheah, Peh Yean; Chan, Eric Chun Yong

    2011-03-30

    Cumulative evidence shows that eicosanoids such as prostaglandins, leukotrienes, thromboxanes and hydroxy eicosatetraenoic acids play an important role in associating inflammation with human colorectal cancer (CRC). In this study an ultra-pressure liquid chromatography/tandem mass spectrometry (UPLC/MS/MS) method was developed and validated for the targeted profiling of eight relevant eicosanoids and the major metabolic precursor, arachidonic acid (AA), in human colon. Multiple reaction monitoring (MRM) experiments were performed in negative electrospray ionization mode. The metabolites were separated using a C(18) column consisting of 1.7 µm ethylene-bridged hybrid particles (100 × 2.1 mm i.d.) and gradient elution (50 to 95% of solvent B) with a mobile phase comprising water (0.1% formic acid) [solvent A] and acetonitrile (0.1% formic acid) [solvent B] at a flow rate of 0.4 mL/min. The analysis time for each sample was 5.5 min. Our UPLC/MS/MS method demonstrated satisfactory validation results in terms of selectivity, sensitivity, matrix effect, linearity, extraction efficiency, intra- and inter-day precision, accuracy and autosampler stability. The method was applied for the clinical profiling of matched pairs of cancerous and normal colon mucosae obtained from eight colorectal cancer patients. Endogenous levels of AA and selected eicosanoids such as prostaglandin E(2) (PGE(2)), prostacyclin (PGI(2)) [assayed as its stable hydrolytic product 6-keto-prostaglandin(1α) (6-k PGF(1α))] and 12-hydroxy-5Z,8Z,10E,14Z-eicosatetraenoic acid (12-HETE) were found to be significantly different (p <0.05; paired t-test) between cancerous and normal mucosae. Copyright © 2011 John Wiley & Sons, Ltd.

  18. Ultra-high-performance liquid chromatography-Time-of-flight high resolution mass spectrometry to quantify acidic drugs in wastewater.

    PubMed

    Becerra-Herrera, Mercedes; Honda, Luis; Richter, Pablo

    2015-12-04

    A novel analytical approach involving an improved rotating-disk sorptive extraction (RDSE) procedure and ultra-high-performance liquid chromatography (UHPLC) coupled to an ultraspray electrospray ionization source (UESI) and time-of-flight mass spectrometry (TOF/MS), in trap mode, was developed to identify and quantify four non-steroidal anti-inflammatory drugs (NSAIDs) (naproxen, ibuprofen, ketoprofen and diclofenac) and two anti-cholesterol drugs (ACDs) (clofibric acid and gemfibrozil) that are widely used and typically found in water samples. The method reduced the amount of both sample and reagents used and also the time required for the whole analysis, resulting in a reliable and green analytical strategy. The analytical eco-scale was calculated, showing that this methodology is an excellent green analysis, increasing its ecological worth. The detection limits (LOD) and precision (%RSD) were lower than 90ng/L and 10%, respectively. Matrix effects and recoveries were studied using samples from the influent of a wastewater treatment plant (WWTP). All the compounds exhibited suppression of their signals due to matrix effects, and the recoveries were approximately 100%. The applicability and reliability of this methodology were confirmed through the analysis of influent and effluent samples from a WWTP in Santiago, Chile, obtaining concentrations ranging from 1.1 to 20.5μg/L and from 0.5 to 8.6μg/L, respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. [Simultaneous determination of seven high risk pesticide residues in royal jelly by high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Li, Yinghong; Zhou, Ping; Xu, Quanhua; Zhao, Huan; Shao, Qiaoyun

    2018-02-08

    A method was developed for the simultaneous determination of seven high risk pesticides in the royal jelly, eg. tau-fluvalinate, triadimenol, coumaphos, haloxyfop, carbendazim, thiophanate-ethyl and thiophanate-methyl by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). First, the royal jelly samples were extracted with acetonitrile under alkaline conditions. After dehydration by anhydrous sodium sulfate, the extracts were enriched and purified through solid-phase extraction (SPE) with Oasis HLB cartridges. Finally, the pesticides were detected by HPLC-MS/MS method. The separation was carried out on a Venusil MP C18 column with gradient elution. Methanol (containing 0.1% (v/v) formic acid) and 0.5 mmol/L ammonium acetate aqueous solution (containing 0.1% (v/v) formic acid) were used as the mobile phases. The detection was achieved using electrospray ionization in positive ion (ESI + ) mode and multiple reaction monitoring (MRM) mode for data collection. Quantification was carried out using internal standard method. The results showed that the seven high risk pesticides were linear in the range of 5-100 μg/kg. The linear correlation coefficients ( r 2 ) were 0.9921-0.9996. The limits of detection (LODs) and limits of quantification (LOQs) of the seven high risk pesticides were 0.5-2.0 μg/kg and 1.0-5.0 μg/kg, respectively. The average recoveries at the three spiked levels were 80.5%-101.3%, and the relative standard deviations were 3.6%-9.4% ( n =3). This method is simple, effective and sensitive, and is suitable for the determination of the pesticide residues in royal jelly.

  20. DETERMINATION OF CARBENDAZIM IN WATER BY HIGH-PERFORMANCE IMMUNOAFFINITY CHROMATOGRAPHY ON-LINE WITH HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY WITH DIODE-ARRAY OR MASS SPECTROMETRIC DETECTION

    EPA Science Inventory

    An automated method for the determination of carbendazim in water that combines high-performance immunoaffinity chromatography (HPIAC), high-performance liquid chromatography (HPLC) in the reversed-phase mode, and detection by either UV-Vis diode array detector (DAD) spectroscopy...

  1. Pressurized planar electrochromatography, high-performance thin-layer chromatography and high-performance liquid chromatography--comparison of performance.

    PubMed

    Płocharz, Paweł; Klimek-Turek, Anna; Dzido, Tadeusz H

    2010-07-16

    Kinetic performance, measured by plate height, of High-Performance Thin-Layer Chromatography (HPTLC), High-Performance Liquid Chromatography (HPLC) and Pressurized Planar Electrochromatography (PPEC) was compared for the systems with adsorbent of the HPTLC RP18W plate from Merck as the stationary phase and the mobile phase composed of acetonitrile and buffer solution. The HPLC column was packed with the adsorbent, which was scrapped from the chromatographic plate mentioned. An additional HPLC column was also packed with adsorbent of 5 microm particle diameter, C18 type silica based (LiChrosorb RP-18 from Merck). The dependence of plate height of both HPLC and PPEC separating systems on flow velocity of the mobile phase and on migration distance of the mobile phase in TLC system was presented applying test solute (prednisolone succinate). The highest performance, amongst systems investigated, was obtained for the PPEC system. The separation efficiency of the systems investigated in the paper was additionally confirmed by the separation of test component mixture composed of six hormones. 2010 Elsevier B.V. All rights reserved.

  2. Characterization of phenolic amides from cortex lycii by ultra high-performance liquid chromatography coupled with LTQ-Orbitrap mass spectrometry

    USDA-ARS?s Scientific Manuscript database

    High performance liquid chromatography (UPLC) and flow injection electrospray ionization with ion trap mass spectrometry (FIMS) fingerprints combined with the principal component analysis (PCA) were examined for their potential in differentiating commercial organic and conventional sage samples. The...

  3. Determination of gymnemagenin in rat plasma using high-performance liquid chromatography-tandem mass spectrometry: application to pharmacokinetics after oral administration of Gymnema sylvestre extract.

    PubMed

    Kamble, Bhagyashree; Gupta, Ankur; Patil, Dada; Khatal, Laxman; Janrao, Shirish; Moothedath, Ismail; Duraiswamy, Basavan

    2013-05-01

    A sensitive and rapid high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method has been developed and validated for the determination of gymnemagenin (GMG), a triterpene sapogenin from Gymnema sylvestre, in rat plasma using withaferin A as the internal standard (IS). Plasma samples were simply extracted using liquid-liquid extraction with tetra-butyl methyl ether. Chromatographic separation was performed on Luna C(18) column using gradient elution of water and methanol (with 0.1% formic acid and 0.3% ammonia) at a flow rate of 0.8 mL/min. GMG and IS were eluted at 4.64 and 4.36 min, ionized in negative and positive mode, respectively, and quantitatively estimated using multiple reaction monitoring (MRM) mode. Two MRM transitions were selected at m/z 505.70 → 455.5 and m/z 471.50 → 281.3 for GMG and IS, respectively. The assay was linear over the concentration range of 5.280-300.920 ng/mL. The mean plasma extraction recoveries for GMG and IS were found to be 80.92 ± 8.70 and 55.63 ± 0.76%, respectively. The method was successfully applied for the determination of pharmacokinetic parameters of GMG after oral administration of G. sylvestre extract. Copyright © 2012 John Wiley & Sons, Ltd.

  4. [Determination of wilforine in honey using solid phase extraction purification and ultra performance liquid chromatography-tanden mas spectrometry].

    PubMed

    Lei, Meikang; Peng, Fang; Ding, Tao; Zhu, Zitong; Xu, Jiawen; Wu, Xiaoqin

    2015-01-01

    A method based on solid phase extraction and ultra performance liquid chromatography coupled with tandem mass spectrometry (SPE-UPLC-MS/MS) has been proposed for the determination of wilforine residue in honey. After the sample was dissolved with water, concentrated and purified by an HLB solid phase extraction cartridge, the UPLC separation was performed on a Hypersil GOLD C18 column (50 mm x 2.1 mm, 1.9 microm) utilizing a gradient elution program of methanol (containing 0.15% formic acid) and water as mobile phases at a flow rate of 0. 25 mL/min. The determination was carried out with electrospray ion source in the positive mode (ESI) and multiple reaction monitoring (MRM) mode. The mass concentration of wilforine in the range of 0.01-2 microg/L was linearly correlated with the peak area, and the correlation coefficients was greater than 0.998. The limit of quantification (S/N>10) for wilforine was 0.01 microg/kg. The recoveries were 76.1% to 96.2% in the spiked levels of 0.01, 0.05 and 0.5 microg/kg with the relative standard deviations (RSD, n=6) lower than 10%. The results indicate that the method is rapid, sensitive and accurate, and can be applied for the qualitative and quantitative analysis of wilforine in honey.

  5. Counter-current chromatography with off-line detection by ultra high performance liquid chromatography/high resolution mass spectrometry in the study of the phenolic profile of Lippia origanoides.

    PubMed

    Leitão, Suzana Guimaraes; Leitão, Gilda Guimarães; Vicco, Douglas K T; Pereira, João Paulo Barreto; de Morais Simão, Gustavo; Oliveira, Danilo R; Celano, Rita; Campone, Luca; Piccinelli, Anna Lisa; Rastrelli, Luca

    2017-10-20

    Lippia origanoides (Verbenaceae) is an important Brazilian medicinal plant, also used for culinary purposes. Most chemical studies with this plant have been focused on its volatile composition. In this work, we combined High-Speed Counter-current Chromatography (HSCCC) and High Performance Liquid Chromatography coupled to Ultra Violet detection and High Resolution Mass Spectrometry (HPLC-UV-HRMS n ) methodologies to access the non-volatile chemical composition of L. origanoides. The crude ethanol extract of L. origanoides (LOEF) was first analyzed by HPLC-UV-HRMS n and allowed the identification of 7 major compounds. Among them, eriodictyol, naringenin and pinocembrin, were determined and are phytochemical markers of this plant. However, owing to the complexity of this plant matrix, LOEF was fractionated by HSCCC (hexane-ethanol-water, 4:3:1) as a tool for preparative pre-purification, affording a flavonoid-rich fraction. A column screening with the chromatographic stationary phases ZIC-HILIC, monolithic and particulate RP18 was performed. The best column separation was achieved with a Purospher STAR RP18e, which was used for HPLC-DAD-HRMS n studies. By this approach 12 compounds were further identified in addition to the major ones identified in the raw extract. Two of them, 6,8-di-C-hexosyl-luteolin and 6,8-di-C-glucosyl-apigenin, are being reported for the first time in the family Verbenaceae. This work shows the integration of HSCCC as a preparative tool for the fractionation and purification of natural products from a complex plant extract with other analytical techniques, with the purpose of showing each technique's potential. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Qualitative and quantitative analysis of the saponins in Panax notoginseng leaves using ultra-performance liquid chromatography coupled with time-of-flight tandem mass spectrometry and high performance liquid chromatography coupled with UV detector.

    PubMed

    Liu, Fang; Ma, Ni; He, Chengwei; Hu, Yuanjia; Li, Peng; Chen, Meiwan; Su, Huanxing; Wan, Jian-Bo

    2018-04-01

    Panax notoginseng leaves (PNL) exhibit extensive activities, but few analytical methods have been established to exclusively determine the dammarane triterpene saponins in PNL. Ultra-performance liquid chromatography coupled with time-of-flight mass spectrometry (UPLC/Q-TOF MS) and HPLC-UV methods were developed for the qualitative and quantitative analysis of ginsenosides in PNL, respectively. Extraction conditions, including solvents and extraction methods, were optimized, which showed that ginsenosides Rc and Rb3, the main components of PNL, are transformed to notoginsenosides Fe and Fd, respectively, in the presence of water, by removing a glucose residue from position C-3 via possible enzymatic hydrolysis. A total of 57 saponins were identified in the methanolic extract of PNL by UPLC/Q-TOF MS. Among them, 19 components were unambiguously characterized by their reference substances. Additionally, seven saponins of PNL-ginsenosides Rb1, Rc, Rb2, and Rb3, and notoginsenosides Fc, Fe, and Fd-were quantified using the HPLC-UV method after extraction with methanol. The separation of analytes, particularly the separation of notoginsenoside Fc and ginsenoside Rc, was achieved on a Zorbax ODS C8 column at a temperature of 35°C. This developed HPLC-UV method provides an adequate linearity ( r 2  > 0.999), repeatability (relative standard deviation, RSD < 2.98%), and inter- and intraday variations (RSD < 4.40%) with recovery (98.7-106.1%) of seven saponins concerned. This validated method was also conducted to determine seven components in 10 batches of PNL. These findings are beneficial to the quality control of PNL and its relevant products.

  7. Investigation of the biotransformation of osthole by liquid chromatography/tandem mass spectrometry.

    PubMed

    Li, Jie; Chan, Wan

    2013-02-23

    Osthole is an active ingredient and one of the major coumarin compounds that were identified in the genus Cnidium moonnieri (L.) Cussion, the fruit of which was used as traditional Chinese medicine to treat male impotence, ringworm infection and blood stasis conventionally. Recent studies revealed that osthole has diverse pharmacological effects, such as improving male sexual dysfunction, anti-diabetes, and anti-hypertentions. The inhibition of thrombosis and platelet aggregation and protection of central nerve were also observed. On the other hand, the metabolism of osthole has not yet been investigated thoroughly. Herein the biotransformation of osthole in rat was investigated after oral administration of osthole by using efficient and sensitive ultra-performance liquid chromatography-tandem quadrupole-time of flight mass spectrometry (UPLC-QTOF/MS). Eighteen osthole metabolites and the parent drug were detected and identified in rat urine. Fourteen metabolites of osthole were identified and characterized for the first time. Structures of metabolites of osthole were elucidated by comparing fragment pattern under MS/MS scan and change of molecular weight with those of osthole. The main phase I metabolic pathways were summed as 7-demethylation, 8-dehydrogenation, hydroxylation on coumarin and 3,4-epoxide. Sulfate conjugates were detected as phase II metabolites of osthole. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. Multi-residue analysis of pharmaceuticals in aqueous environmental samples by online solid-phase extraction-ultra-high-performance liquid chromatography-tandem mass spectrometry: optimisation and matrix effects reduction by quick, easy, cheap, effective, rugged and safe extraction.

    PubMed

    Bourdat-Deschamps, Marjolaine; Leang, Sokha; Bernet, Nathalie; Daudin, Jean-Jacques; Nélieu, Sylvie

    2014-07-04

    The aim of this study was to develop and optimise an analytical method for the quantification of a bactericide and 13 pharmaceutical products, including 8 antibiotics (fluoroquinolones, tetracyclines, sulfonamides, macrolide), in various aqueous environmental samples: soil water and aqueous fractions of pig slurry, digested pig slurry and sewage sludge. The analysis was performed by online solid-phase extraction coupled to ultra-high performance liquid chromatography with tandem mass spectrometry (online SPE-UHPLC-MS-MS). The main challenge was to minimize the matrix effects observed in mass spectrometry, mostly due to ion suppression. They depended on the dissolved organic carbon (DOC) content and its origin, and ranged between -22% and +20% and between -38% and -93% of the signal obtained without matrix, in soil water and slurry supernatant, respectively. The very variable levels of these matrix effects suggested DOC content cut-offs above which sample purification was required. These cut-offs depended on compounds, with concentrations ranging from 30 to 290mgC/L for antibiotics (except tylosine) up to 600-6400mgC/L for the most apolar compounds. A modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction procedure was therefore optimised using an experimental design methodology, in order to purify samples with high DOC contents. Its performance led to a compromise, allowing fluoroquinolone and tetracycline analysis. The QuEChERS extraction salts consisted therefore of sodium acetate, sodium sulfate instead of magnesium sulfate, and sodium ethylenediaminetetraacetate (EDTA) as a ligand of divalent cations. The modified QuEChERS procedure employed for the extraction of pharmaceuticals in slurry and digested slurry liquid phases reduced the matrix effects for almost all the compounds, with extraction recoveries generally above 75%. The performance characteristics of the method were evaluated in terms of linearity, intra-day and inter

  9. Proteomic analysis of Taenia ovis metacestodes by high performance liquid chromatography-coupled tandem mass spectrometry.

    PubMed

    Zheng, Yadong

    2017-03-15

    Taenia ovis metacestodes reside in the muscle of sheep and goats, and may cause great economic loss due to condemnation of carcasses if not effectively controlled. Although advances have been made in the control of T. ovis infection, our knowledge of T. ovis biology is limited. Herein the protein profiling of T. ovis metacestodes was determined by liquid chromatography-linked tandem mass spectrometry. A total of 966 proteins were identified and 25.1% (188/748) were annotated to be associated with metabolic pathways. Consistently, GO analysis returned a metabolic process (16.27%) as one of two main biological process terms. Moreover, it was found that 24 proteins, including very low-density lipoprotein receptor, enolase, paramyosin and endophilin B1, were abundant in T. ovis metacestodes. These proteins may be associated with motility, metabolism, signaling, stress, drug resistance and immune responses. Furthermore, comparative analysis of 5 cestodes revealed the presence of Taenia-specific enolases. These data provide clues for better understanding of T. ovis biology, which is informative for effective control of infection. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Effect of six Chinese spices on heterocyclic amine profiles in roast beef patties by ultra performance liquid chromatography-tandem mass spectrometry and principal component analysis.

    PubMed

    Zeng, Maomao; He, Zhiyong; Zheng, Zongping; Qin, Fang; Tao, Guanjun; Zhang, Shuang; Gao, Yahui; Chen, Jie

    2014-10-08

    The effects of Chinese spices on the profiles of 17 heterocyclic amines (HAs) from seven HA categories were investigated in roast beef patties using Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry (UPLC-MS/MS) and principal component analysis. Three groups of HAs, imidazopyridines (PhIP, DMIP, and 1,5,6-TMIP), imidazoquinoxalines (MeIQx and 4,8-DiMeIQx), and β-carbolines (harman and norharman), were detected and quantified in all of the samples. The results demonstrated that the total HA and imidazopyridine profiles could clearly be affected by 1% pricklyash peel (14.1 ± 0.76 and 6.06 ± 0.32 ng/g), chilli (41.0 ± 0.01 and 23.0 ± 0.52 ng/g), and cumin (59.9 ± 2.44 and 31.1 ± 3.06 ng/g), in comparison with control values of 21.8 ± 2.40 and 14.3 ± 2.04 ng/g, respectively. The difference was only significant (p < 0.05) for cumin. The imidazoquinoxaline profile was significantly (p < 0.05) affected by 1% pricklyash peel (0.57 ± 0.05 ng/g) and cumin (2.36 ± 0.20 ng/g) compared to the control (1.16 ± 0.11 ng/g). The β-carboline profile was only markedly (p < 0.05) affected by 1% cumin (26.4 ± 0.82 ng/g) compared to the control (6.26 ± 0.26 ng/g). In general, pricklyash peel inhibited HA formation, whereas star anise, fennel, cumin, chilli, and black pepper promoted HA formation. The findings could facilitate the selection of spices in meat processing to minimize HA formation.

  11. Biomarker analysis of hemoglobin adducts of acrylamide and glycidamide enantiomers for mid-term internal exposure assessment by isotope dilution ultra-high performance liquid chromatography tandem mass spectrometry.

    PubMed

    Zhang, Yu; Wang, Qiao; Zhang, Gong; Jia, Wei; Ren, Yiping; Wu, Yongning

    2018-02-01

    Hemoglobin (Hb) adducts of acrylamide (AA) and its oxidative metabolite glycidamide (GA) are important biomarkers for evaluating the mid-term exposure of acrylamide toxicity in vivo. Taking pentafluoro-2-methylphenyl isothiocyanates of N-(2-carbamoylethyl)valine (AAVal-PFPTH) and N-(2-carbamoyl-2-hydroxyethy)valine (GAVal-PFPTH) as target analytes, we developed an isotope dilution ultra-high performance liquid chromatograph tandem mass spectrometry (UHPLC-MS/MS) method for the simultaneous determination of AA and GA hemoglobin (Hb) adducts under the electroscopy ionization negative (ESI‾) mode in the present work. Among them, the enantiomer pair of GA-Hb adducts was firstly identified and successfully separated at baseline level. The method achieved high sensitivity with the LOD and LOQ ranging 1.43-5.05pmol/g Hb and 4.78-16.82pmol/g Hb, respectively. The recovery rates with low, intermediate and high spiking levels were calculated as 97.0-105.2%, 97.4-106.4% and 100.3-111.2%, respectively. Acceptable within-laboratory reproducibility (RSD < 13.7%) substantially supported the robustness of current UHPLC-MS/MS method, which was successfully applied to measure the hemoglobin adducts of acrylamide and glycidamide enantiomers in blood of both rats and humans. A linear exposure assessment model was developed for estimating the daily exposure to acrylamide in humans via considering acrylamide hemoglobin adducts as variables, indicating a novel connect between biomarker-based internal exposure and dietary-based external exposure. Overall, the present instrumental analysis and related internal exposure assessment model provide a substantially methodological support for profiling the internal biological exposure and estimating the external dietary exposure to acrylamide. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Residue analysis and degradation studies of fenbuconazole and myclobutanil in strawberry by chiral high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhang, Hu; Wang, Xinquan; Qian, Mingrong; Wang, Xiangyun; Xu, Hao; Xu, Mingfei; Wang, Qiang

    2011-11-23

    A simple and sensitive enantioselective method for the determination of fenbuconazole and myclobutanil in strawberry was developed by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Fenbuconazole and myclobutanil residues in strawberry were extracted with acetonitrile containing 1% acetic acid, and an aliquot was cleaned up with PSA (primary and secondary amine) and C(18) sorbent. The direct resolution of fenbuconazole and myclobutanil enantiomers was performed on a cellulose tris (3,5-dimethylphenylcarbamate) column using acetonitrile-0.1% formic acid solution (60:40, v/v) as the mobile phase. Quantification was achieved using matrix-matched standard calibration curves, and the limits of quantification for fenbuconazole and myclobutanil enantiomers in strawberry were both 2 μg/kg. The method was successfully utilized to investigate the probable enantioselective degradation of fenbuconazole and myclobutanil in strawberry. The results showed that the degradation of the fenbuconazole and myclobutanil enantiomers in strawberry followed pseudofirst-order kinetics (R(2) > 0.97). The results from this study revealed that the degradation of fenbuconazole in strawberry was not enantioselective, while the degradation of myclobutanil was enantioselective, and the (+)-myclobutanil showed a faster degradation than (-)-myclobutanil in strawberry, resulting in the relative enrichment of (-)-myclobutanil in residue. The results could provide a reference to fully evaluate the risks of these two fungicides.

  13. Solution for blank and matrix difficulties encountered during phthalate analysis of edible oils by high performance liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Vavrouš, Adam; Pavloušková, Jana; Ševčík, Václav; Vrbík, Karel; Čabala, Radomír

    2016-07-22

    Worldwide production of phthalates has led to their undesirable presence in the food chain. Particularly edible oils have become an area of growing concern owing to numerous reported occurrences of phthalates. The analytical methods used in this field face difficulties associated mainly with matrix complexity or phthalate contamination which this study has aimed to describe and resolve. The proposed procedure consisting of liquid-liquid extraction, solid phase extraction and high performance liquid chromatography coupled with tandem mass spectrometry allowed us to analyze simultaneously 6 individual phthalates and 2 phthalate isomeric mixtures. DSC-18 SPE phase was selected for cleanup owing to the most efficient co-extract removal (assessed using high resolution mass spectrometry). Several sources of phthalate contamination were identified, however, the mobile phase was the most serious. The key improvement was achieved by equipping a contamination trap, a 50-mm reverse phase HPLC column, generating a delay between target and mobile phase peaks of the same compounds. RSDs ranging between 2.4 and 16 % confirm good precision and LOQs between 5.5 and 110μgkg(-1) reflect satisfactory blank management. With up to 19 occurrences in 25 analyzed edible oil samples and levels up to 33mgkg(-1), bis(2-ethylhexyl), diisononyl and diisodecyl phthalates were the most important contaminants. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. A quantitative, selective and fast ultra-high performance liquid chromatography tandem mass spectrometry method for the simultaneous analysis of 33 basic drugs in hair (amphetamines, cocaine, opiates, opioids and metabolites).

    PubMed

    Fernández, María Del Mar Ramírez; Di Fazio, Vincent; Wille, Sarah M R; Kummer, Natalie; Samyn, Nele

    2014-08-15

    Forensic testing for drugs of abuse in hair has become a useful diagnostic tool in determining chronic drug use as well as examining long-term drug history thorough segmental analysis. However, sensitive and specific analytical methods are needed. A simple, rapid and highly sensitive and specific method for the extraction and quantification of 33 opioids, opiates, cocaine, and amphetamines is presented. The method was fully validated according to international guidelines. Twenty milligrams of hair sample was pulverized and then incubated in the same disposable tube with methanol (under sonication at 45°C) during 4h. After centrifugation the supernatant was evaporated up to about 100 μL and a solid phase extraction (SPE) followed by separation and quantification using ultra performance liquid chromatography-tandem mass spectrometry (UHLC-MS/MS) were carried out. Chromatographic separation was achieved using a BEH phenyl column eluted with 0.1% formic acid: methanol (0.1% formic acid). Selectivity of the method was achieved by a combination of retention time, and two precursor-product ion transitions. Good intra-assay and inter-assay precision (relative standard deviations (RSDs) were observed (<15%) for most of the compounds. The lower limit of quantification was fixed at the lowest calibrator in the linearity experiments and it ranged from 0.006 to 0.063 ng/mg. No instability was observed in processed samples. Extraction efficiency varied from 37 to 107% (except for EDDP with a recovery of 5%) and matrix effects ranged from 52 to 160%, and for most of the compounds it was compensated by the internal standard (IS). The method was subsequently applied to authentic hair samples obtained from forensic and toxicology cases and to proficiency test (obtaining z-scores lower than 1 for most of the compounds). The validation and actual sample analysis results show that this method is rugged, precise, accurate, and well-suited for routine hair analysis. Copyright © 2014

  15. Simultaneous determination of four aflatoxins and ochratoxin A in ginger after inoculation with fungi by ultra-fast liquid chromatography-tandem mass spectrometry.

    PubMed

    Yang, Ying; Wen, Jing; Kong, Weijun; Liu, Qiutao; Luo, Hongli; Wang, Jian; Yang, Meihua

    2016-09-01

    Aflatoxins (AFs) and ochratoxin A (OTA) have been detected frequently in food, agricultural products and traditional Chinese medicines, and their presence poses serious health and economic problems worldwide. Ginger can easily be polluted with mycotoxins. In this study, ginger samples were cultivated for 15 days after inoculation with fungi and were prepared based on ultrasound-assisted solid-liquid extraction using methanol/water followed by immunoaffinity column clean-up and analysed by ultra-fast liquid chromatography-tandem mass spectrometry (UFLC-MS/MS) for AFs and OTA. The limits of detection and quantification of AFs and OTA were 0.04-0.30 µg mL(-1) and 0.125-1.0 µg mL(-1) , respectively. The recoveries were 82.0-100.2%. After 15 days' cultivation, no macroscopic mildew was found in ginger. But, the content of AFB1 expressed an increasing trend in ginger, peel [less than the limit of quantification (LOQ)] to the innermost layer (51.86 µ mL(-1) ), AFB2 was only detected in the innermost layer at the level of 0.87 µ mL(-1) . A small amount (high sensitivity. Meanwhile, in practice, more attention should be paid to the safety and quality of ginger. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  16. Ultra-sensitive assay for paclitaxel in intracellular compartments of A549 cells using liquid chromatography-tandem mass spectrometry.

    PubMed

    Wang, Tingting; Ma, Wenxiao; Sun, Yantong; Yang, Yan; Zhang, Weiping; Fawcett, J Paul; Du, Hongwei; Gu, Jingkai

    2013-01-01

    A high-performance liquid chromatography-tandem mass spectrometric (LC-MS/MS) method for the determination of paclitaxel in intracellular compartments using docetaxel as internal standard (IS) has been developed and validated. A549 cancer cells (10(6)) were incubated with paclitaxel (2ng/mL) for up to 4h and then subjected to sequential extraction of cytosolic, membrane/organelle, nuclear and cytoskeleton soluble protein. Fractions were ultrasonicated to release protein bound paclitaxel after which drug was extracted using liquid-liquid extraction with diethyl ether:dichloromethane (2:1, v/v). Chromatographic separation was then carried out on an Ascentis Express C18 column (50mm×4.6mm, 2.7μm) with a mobile phase of acetonitrile:0.1% formic acid in water (50:50, v/v). Detection involved electrospray positive ionization followed by multiple reactions monitoring of the precursor-to-product ion transitions of paclitaxel at m/z 854.4→286.3 and docetaxel at m/z 808.6→226.1. Assay validation based on samples of total cell extract in the same buffer as protein fractions showed the assay was linear over the range 2-600pg/mL with intra- and inter-day precision (as relative standard deviation) and accuracy (as relative error) of <7% and <±12%, respectively. Recovery was approximately 70% and matrix effects were minimal. The distribution of paclitaxel in subcellular components of A549 cancer cells was mainly into the cytoskeletal compartment. Copyright © 2012 Elsevier B.V. All rights reserved.

  17. A dispersive liquid-liquid micellar microextraction for the determination of pharmaceutical compounds in wastewaters using ultra-high-performace liquid chromatography with DAD detection.

    PubMed

    Montesdeoca-Esponda, Sarah; Mahugo-Santana, Cristina; Sosa-Ferrera, Zoraida; Santana-Rodríguez, José Juan

    2015-03-01

    A dispersive liquid-liquid micellar microextraction (DLLMME) method coupled with ultra-high-performance liquid chromatography (UHPLC) using Diode Array Detector (DAD) detector was developed for the analysis of five pharmaceutical compounds of different nature in wastewaters. A micellar solution of a surfactant, polidocanol, as extraction solvent (100 μL) and chloroform as dispersive solvent (200 μL) were used to extract and preconcentrate the target analytes. Samples were heated above critical temperature and the cloudy solution was centrifuged. After removing the chloroform, the reduced volume of surfactant was then injected in the UHPLC system. In order to obtain high extraction efficiency, the parameters affecting the liquid-phase microextraction, such as time and temperature extraction, ionic strength and surfactant and organic solvent volume, were optimized using an experimental design. Under the optimized conditions, this procedure allows enrichment factors of up to 47-fold. The detection limit of the method ranged from 0.1 to 2.0 µg/L for the different pharmaceuticals. Relative standard deviations were <26% for all compounds. The procedure was applied to samples from final effluent collected from wastewater treatment plants in Las Palmas de Gran Canaria (Spain), and two compounds were measured at 67 and 113 µg/L in one of them. Copyright © 2014 John Wiley & Sons, Ltd.

  18. High performance liquid chromatography: Tandem mass spectrometric determination of cisplatin levels in different visceral pleura layers of rats.

    PubMed

    Xia, Hui; Zhang, Wen; Li, Yingjie; Yu, Changhai

    2015-05-01

    The aim of the present study was to investigate the concentration of cisplatin in different layers of the visceral pleura in rats, following drug administration. In this study, a sensitive and specific liquid chromatography method coupled with electrospray ionization-tandem mass spectrometry was established to investigate the disposition of cisplatin in different layers of the visceral pleura in rats. Methodological data, including specificity, linearity, accuracy, recovery, precision and lower limits of quantification, confirmed that this novel method may be used to efficiently quantify the cisplatin concentrations in visceral pleura of rats following administration of the drug. Furthermore, the results demonstrated that the desired drug concentration was not achieved in the outer or inner elastic layers of the visceral pleura following injection with cisplatin through various administration methods.

  19. Simultaneous determination of three pesticides and their metabolites in unprocessed foods using ultraperformance liquid chromatography-tandem mass spectrometry.

    PubMed

    Rong, Lili; Wu, Xiaohu; Xu, Jun; Dong, Fengshou; Liu, Xingang; Pan, Xinglu; Du, Pengqiang; Wei, Dongmei; Zheng, Yongquan

    2018-02-01

    We have developed a rapid, multi-compound analytical method for measuring residues of the pesticides thiamethoxam and its metabolite, clothianidin; fipronil and its three metabolites, fipronil sulfone, fipronil sulfide, and fipronil desulfinyl; and pyraclostrobin in unprocessed foods (rice, corn, cucumbers, tomatoes, apples, and bananas) by ultra-performance liquid chromatography coupled to tandem mass spectrometry. Acetonitrile was used as the extraction solvent, and an octadecylsilane-dispersive SPE was used to clean up the analytes, which were then separated through a UPLC HSS T3 column connected to a tandem mass spectrometer via an electrospray ionisation source. The linearity of this method for the target analytes was excellent (R 2  ≥0.990) in the concentration range of 5-1000 μg kg -1 . The average recoveries of the seven compounds at concentrations of 10, 100, and 1000 μg kg -1 from six spiked matrix samples ranged from 73.6 to 110.6%, all with RSD values of ≤19.7%. The limit of quantification was 10 μg kg -1 . The method validated the effectiveness of the method for routine monitoring the residue of these pesticides and their metabolites in foods.

  20. Residue analysis and persistence evaluation of fipronil and its metabolites in cotton using high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Wu, Xiaohu; Yu, Yang; Xu, Jun; Dong, Fengshou; Liu, Xingang; Du, Pengqiang; Wei, Dongmei; Zheng, Yongquan

    2017-01-01

    A simple residue analytical method based on the QuEChERS approach and high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) detection was developed for the analysis of fipronil and its three metabolites in cottonseed, cotton plant and soil. The average recoveries of four test compounds from all three matrices were 78.6-108.9% at the level of 0.005 to 0.5 mg/kg, with an RSD in the range of 0.6 to 13.7%. The limit of quantification (LOQ) of the four test compounds ranged from 0.005 to 0.01 mg/kg. The results of the residual dynamics experiments showed that fipronil dissipated rapidly in cotton plants and soil and that oxidation and photolysis were the main degradation pathways. Moreover, the bi-exponential models demonstrated a good fit of the measured data for fipronil in cotton plants and soil, with R2 in the range of 0.8989 to 0.9989. Furthermore, a total of 40 samples of cottonseed from Shandong Province were analyzed, and all of the samples were free from the four test compound residues.

  1. Residue analysis and persistence evaluation of fipronil and its metabolites in cotton using high-performance liquid chromatography-tandem mass spectrometry

    PubMed Central

    Wu, Xiaohu; Yu, Yang; Xu, Jun; Dong, Fengshou; Liu, Xingang; Du, Pengqiang; Wei, Dongmei; Zheng, Yongquan

    2017-01-01

    A simple residue analytical method based on the QuEChERS approach and high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) detection was developed for the analysis of fipronil and its three metabolites in cottonseed, cotton plant and soil. The average recoveries of four test compounds from all three matrices were 78.6–108.9% at the level of 0.005 to 0.5 mg/kg, with an RSD in the range of 0.6 to 13.7%. The limit of quantification (LOQ) of the four test compounds ranged from 0.005 to 0.01 mg/kg. The results of the residual dynamics experiments showed that fipronil dissipated rapidly in cotton plants and soil and that oxidation and photolysis were the main degradation pathways. Moreover, the bi-exponential models demonstrated a good fit of the measured data for fipronil in cotton plants and soil, with R2 in the range of 0.8989 to 0.9989. Furthermore, a total of 40 samples of cottonseed from Shandong Province were analyzed, and all of the samples were free from the four test compound residues. PMID:28291815

  2. Quantification of Quercetin and Rutin from Benincasa hispida Seeds and Carissa Congesta Roots by High-performance Thin Layer Chromatography and High-performance Liquid Chromatography.

    PubMed

    Doshi, Gaurav Mahesh; Une, Hemant Devidas

    2016-01-01

    In Indian Ayurvedic system, Benincasa hispida (BH) and Carissa congesta (CC) are well-known plants used for major and minor ailments. BH has been regarded as Kushmanda, whereas CC has been used in immune-related disorders of the human system. Quercetin and rutin identified from the vast plethora of plant extracts have proved to possess ethnopharmacological relevance. In present studies, we have determined quercetin and rutin in terms of percentage in BH seeds and CC roots by high-performance thin layer chromatography (HPTLC) and high-performance liquid chromatography (HPLC). After extraction and phytochemical screening, the extracts were subjected to quantification for the presence of quercetin and rutin by HPTLC and HPLC. HPTLC showed quercetin as 44.60, 27.13% and rutin as 32.00, 36.31% w/w, whereas HPLC revealed quercetin as 34.00, 35.00% and rutin as 21.99, 45.03% w/v in BH and CC extracts, respectively. The BH and CC extracts have elucidated peaks that were corresponding with standard peaks on undertaking chromatographic studies. Quercetin and rutin are isolated from BH seeds and CC roots by High Performance. Thin Layer Chromatography and High Performance Liquid Chromatography. HPTLC revealed presence of quercetin as 44.60, 27.13 % and rutin as 32.00, 36.31 % w/w. HPLC revealed presence of quercetin as 34.00, 35.00 % and rutin as 21.99, 45.03 % w/v. Abbreviation Used: HPTLC: High Performance Thin Layer Chromatography; HPLC: High Pressure Liquid Chromatography, UV: Ultraviolet, CC: Carissa congesta, BH: Benincasa hispida.

  3. Quantification of Quercetin and Rutin from Benincasa hispida Seeds and Carissa Congesta Roots by High-performance Thin Layer Chromatography and High-performance Liquid Chromatography

    PubMed Central

    Doshi, Gaurav Mahesh; Une, Hemant Devidas

    2016-01-01

    Objective: In Indian Ayurvedic system, Benincasa hispida (BH) and Carissa congesta (CC) are well-known plants used for major and minor ailments. BH has been regarded as Kushmanda, whereas CC has been used in immune-related disorders of the human system. Quercetin and rutin identified from the vast plethora of plant extracts have proved to possess ethnopharmacological relevance. Materials and Methods: In present studies, we have determined quercetin and rutin in terms of percentage in BH seeds and CC roots by high-performance thin layer chromatography (HPTLC) and high-performance liquid chromatography (HPLC). After extraction and phytochemical screening, the extracts were subjected to quantification for the presence of quercetin and rutin by HPTLC and HPLC. Results: HPTLC showed quercetin as 44.60, 27.13% and rutin as 32.00, 36.31% w/w, whereas HPLC revealed quercetin as 34.00, 35.00% and rutin as 21.99, 45.03% w/v in BH and CC extracts, respectively. Conclusion: The BH and CC extracts have elucidated peaks that were corresponding with standard peaks on undertaking chromatographic studies. SUMMARY Quercetin and rutin are isolated from BH seeds and CC roots by High Performance. Thin Layer Chromatography and High Performance Liquid Chromatography. HPTLC revealed presence of quercetin as 44.60, 27.13 % and rutin as 32.00, 36.31 % w/w. HPLC revealed presence of quercetin as 34.00, 35.00 % and rutin as 21.99, 45.03 % w/v. Abbreviation Used: HPTLC: High Performance Thin Layer Chromatography; HPLC: High Pressure Liquid Chromatography, UV: Ultraviolet, CC: Carissa congesta, BH: Benincasa hispida PMID:26941534

  4. Investigation of the persistence of nerve agent degradation analytes on surfaces through wipe sampling and detection with ultrahigh performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Willison, Stuart A

    2015-01-20

    The persistence of chemical warfare nerve agent degradation analytes on surfaces is important, from indicating the presence of nerve agent on a surface to guiding environmental restoration of a site after a release. Persistence was investigated for several chemical warfare nerve agent degradation analytes on indoor surfaces and presents an approach for wipe sampling of surfaces, followed by wipe extraction and liquid chromatography-tandem mass spectrometry detection. Commercially available wipe materials were investigated to determine optimal wipe recoveries. Tested surfaces included porous/permeable (vinyl tile, painted drywall, and wood) and largely nonporous/impermeable (laminate, galvanized steel, and glass) surfaces. Wipe extracts were analyzed by ultrahigh performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). UPLC provides a separation of targeted degradation analytes in addition to being nearly four times faster than high-performance liquid chromatography, allowing for greater throughput after a large-scale contamination incident and subsequent remediation events. Percent recoveries from nonporous/impermeable surfaces were 60-103% for isopropyl methylphosphonate (IMPA), GB degradate; 61-91% for ethyl methylphosphonate (EMPA), VX degradate; and 60-98% for pinacolyl methylphosphonate (PMPA), GD degradate. Recovery efficiencies for methyl phosphonate (MPA), nerve agent degradate, and ethylhydrogen dimethylphosphonate (EHDMAP), GA degradate, were lower, perhaps due to matrix effects. Diisopropyl methylphosphonate, GB impurity, was not recovered from surfaces. The resulting detection limits for wipe extracts were 0.065 ng/cm(2) for IMPA, 0.079 ng/cm(2) for MPA, 0.040 ng/cm(2) for EMPA, 0.078 ng/cm(2) for EHDMAP, and 0.013 ng/cm(2) for PMPA. The data indicate that laboratories may hold wipe samples for up to 30 days prior to analysis. Target analytes were observed to persist on surfaces for at least 6 weeks.

  5. Analysis of mexicanolide- and phragmalin-type limonoids from Heynea trijuga using high-performance liquid chromatography/electrospray tandem mass spectrometry.

    PubMed

    Yang, Wei; Fang, Dong-Mei; He, Hong-Ping; Hao, Xiao-Jiang; Wu, Zhi-Jun; Zhang, Guo-Lin

    2013-06-15

    Limonoids, a class of tetranortriterpenoids, exhibit various biological effects, including acting as potent antifeedants and insect growth-regulators against various pests. The analysis of phragmalin- and mexicanolide-type limonoids by collision-induced dissociation tandem mass spectrometry (CID-MS/MS) has not been reported. A high-performance liquid chromatography/electrospray ionization (HPLC/ESI)-MS/MS method was developed to investigate the fragmentation patterns of [M+NH4 ](+) ions for nine reference phragmalin- and mexicanolide-type limonoids. The method was also used in the identification of limonoid compounds in botanic extracts of Heynea trijuga. The losses of side chains and the furan part were the major fragmentation patterns. However, there was variation in the relative abundances of product ions resulting from the same fragmentation pathways. A total of 89 phragmalin- and mexicanolide-type limonoids in botanic extracts of Heynea trijuga were detected and 50 of these compounds were identified or tentatively characterized based on elemental constituents, fragmentation pathways, and the profile of the major product ions of reference compounds. In addition, the isomers could be tentatively distinguished. An HPLC/ESI-MS/MS method was developed and could be used to simultaneously identify and screen phragmalin- and mexicanolide-type limonoids in botanic extracts of Heynea trijuga. Copyright © 2013 John Wiley & Sons, Ltd.

  6. Simultaneous high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS-MS) analysis of cyanide and thiocyanate from swine plasma.

    PubMed

    Bhandari, Raj K; Manandhar, Erica; Oda, Robert P; Rockwood, Gary A; Logue, Brian A

    2014-01-01

    An analytical procedure for the simultaneous determination of cyanide and thiocyanate in swine plasma was developed and validated. Cyanide and thiocyanate were simultaneously analyzed by high-performance liquid chromatography tandem mass spectrometry in negative ionization mode after rapid and simple sample preparation. Isotopically labeled internal standards, Na(13)C(15)N and NaS(13)C(15)N, were mixed with swine plasma (spiked and nonspiked), proteins were precipitated with acetone, the samples were centrifuged, and the supernatant was removed and dried. The dried samples were reconstituted in 10 mM ammonium formate. Cyanide was reacted with naphthalene-2,3-dicarboxaldehyde and taurine to form N-substituted 1-cyano[f]benzoisoindole, while thiocyanate was chemically modified with monobromobimane to form an SCN-bimane product. The method produced dynamic ranges of 0.1-50 and 0.2-50 μM for cyanide and thiocyanate, respectively, with limits of detection of 10 nM for cyanide and 50 nM for thiocyanate. For quality control standards, the precision, as measured by percent relative standard deviation, was below 8 %, and the accuracy was within ±10 % of the nominal concentration. Following validation, the analytical procedure successfully detected cyanide and thiocyanate simultaneously from the plasma of cyanide-exposed swine.

  7. Simultaneous quantification of 5 main components of Psoralea corylifolia L. in rats' plasma by utilizing ultra high pressure liquid chromatography tandem mass spectrometry.

    PubMed

    Gao, Qianqian; Xu, Zisheng; Zhao, Genhua; Wang, Heng; Weng, Zebin; Pei, Ke; Wu, Li; Cai, Baochang; Chen, Zhipeng; Li, Weidong

    2016-02-01

    Psoralea corylifolia L. has long been used in traditional Chinese medicine for treating and preventing many diseases. A group of flavonoid components are regarded as the active principals within the seeds. In this research, a rapid, accurate and sensitive ultra high pressure liquid chromatography tandem mass spectrometry (UHPLC/MS/MS) method has been established for simultaneous quantification of its 5 main components, namely, neobavaisoflavone, bavachin, isobavachalcone, bavachinin and corylifol A in rats' plasma after the rats were orally administrated with Buguzhi extract. Negative ion electrospray mode was applied in the detection process. Multiple reactions monitoring (MRM) mode was utilized for simultaneous quantitative analyzing of neobavaisoflavone (m/z 321.1→m/z 265.1), bavachin (m/z 323.1→m/z 119.0), isobavachalcone (m/z 323.2→m/z 119.0), bavachinin (m/z 337.2→m/z 119.0), corylifol A (m/z 389.2→m/z 277.0) and liquiritigenin (Internal Standard, m/z 255.1→m/z 119.0). Chromatographic separation of the above mentioned components was conducted on a Waters BEH-C18 column (100 mm×2.1mm, 1.7μm) with gradient elution system at flow rate of 0.3mL/min. The mobile phase was composed of acetonitrile and 0.1% formic acid solution. The lower limit of quantification (LLOQ) for each of the above analytes was 0.5ng/mL. Each of the analytes exhibited good linearity within the concentration range of 0.5-100ng/mL. The method was fully validated for its selectivity, accuracy, precision, stability, matrix effect and extraction recovery. The validated method has been successfully applied for simultaneous determination of the 5 flavonoids in rat plasma for the first time. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Quality evaluation of moluodan concentrated pill using high-performance liquid chromatography fingerprinting coupled with chemometrics.

    PubMed

    Tao, Lingyan; Zhang, Qing; Wu, Yongjiang; Liu, Xuesong

    2016-12-01

    In this study, a fast and effective high-performance liquid chromatography method was developed to obtain a fingerprint chromatogram and quantitative analysis simultaneously of four indexes including gallic acid, chlorogenic acid, albiflorin and paeoniflorin of the traditional Chinese medicine Moluodan Concentrated Pill. The method was performed by using a Waters X-bridge C 18 reversed phase column on an Agilent 1200S high-performance liquid chromatography system coupled with diode array detection. The mobile phase of the high-performance liquid chromatography method was composed of 20 mmol/L phosphate solution and acetonitrile with a 1 mL/min eluent velocity, under a detection temperature of 30°C and a UV detection wavelength of 254 nm. After the methodology validation, 16 batches of Moluodan Concentrated Pill were analyzed by this high-performance liquid chromatography method and both qualitative and quantitative evaluation results were achieved by similarity analysis, principal component analysis and hierarchical cluster analysis. The results of these three chemometrics were in good agreement and all indicated that batch 10 and batch 16 showed significant differences with the other 14 batches. This suggested that the developed high-performance liquid chromatography method could be applied in the quality evaluation of Moluodan Concentrated Pill. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Putative identification of new p-coumaroyl glycoside flavonoids in grape by ultra-high performance liquid chromatography/high-resolution mass spectrometry.

    PubMed

    Panighel, Annarita; De Rosso, Mirko; Dalla Vedova, Antonio; Flamini, Riccardo

    2015-02-28

    Grape polyphenols are antioxidant compounds, markers in vine chemotaxonomy, and involved in color stabilization of red wines. Sugar acylation usually confers higher stability on glycoside derivatives and this effect is enhanced by an aromatic substituent such as p-coumaric acid. Until now, only p-coumaroyl anthocyanins have been found in grape. A method of 'suspect screening analysis' by ultra-high-performance liquid chromatography/high-resolution mass spectrometry (UHPLC/QTOFMS) has recently been developed to study grape metabolomics. In the present study, this approach was used to identify new polyphenols in grape by accurate mass measurement, MS/MS fragmentation, and study of correlations between fragments observed and putative structures. Three putative p-coumaroyl flavonoids were identified in Raboso Piave grape extract: a dihydrokaempferide-3-O-p-coumaroylhexoside-like flavanone, isorhamnetin-3-O-p-coumaroylglucoside, and a chrysoeriol-p-coumaroylhexoside-like flavone. Accurate MS provided structural characterization of functional groups, and literature data indicates their probable position in the molecule. A fragmentation scheme is proposed for each compound. Compounds were identified by overlapping various analytical methods according to recommendations in the MS-based metabolomics literature. Stereochemistry and the definitive position of substituents in the molecule can only be confirmed by isolation and characterization or synthesis of each compound. These findings suggest addressing research of acylated polyphenol glycosides to other grape varieties. Copyright © 2015 John Wiley & Sons, Ltd.

  10. Determination and fingerprint analysis of steroidal saponins in roots of Liriope muscari (Decne.) L. H. Bailey by ultra high performance liquid chromatography coupled with ion trap time-of-flight mass spectrometry.

    PubMed

    Li, Yong-Wei; Qi, Jin; Wen-Zhang; Zhou, Shui-Ping; Yan-Wu; Yu, Bo-Yang

    2014-07-01

    Liriope muscari (Decne.) L. H. Bailey is a well-known traditional Chinese medicine used for treating cough and insomnia. There are few reports on the quality evaluation of this herb partly because the major steroid saponins are not readily identified by UV detectors and are not easily isolated due to the existence of many similar isomers. In this study, a qualitative and quantitative method was developed to analyze the major components in L. muscari (Decne.) L. H. Bailey roots. Sixteen components were deduced and identified primarily by the information obtained from ultra high performance liquid chromatography with ion-trap time-of-flight mass spectrometry. The method demonstrated the desired specificity, linearity, stability, precision, and accuracy for simultaneous determination of 15 constituents (13 steroidal glycosides, 25(R)-ruscogenin, and pentylbenzoate) in 26 samples from different origins. The fingerprint was established, and the evaluation was achieved using similarity analysis and principal component analysis of 15 fingerprint peaks from 26 samples by ultra high performance liquid chromatography. The results from similarity analysis were consistent with those of principal component analysis. All results suggest that the established method could be applied effectively to the determination of multi-ingredients and fingerprint analysis of steroid saponins for quality assessment and control of L. muscari (Decne.) L. H. Bailey. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Determination of caffeoylquinic acids in feed and related products by focused ultrasound solid-liquid extraction and ultra-high performance liquid chromatography-mass spectrometry.

    PubMed

    Tena, M T; Martínez-Moral, M P; Cardozo, P W

    2015-06-26

    A method to determine caffeoylquinic acids (CQAs) in three sources (herbal extract, feed additive and finished feed) using for the first time focused ultrasound solid-liquid extraction (FUSLE) followed by ultra-high performance liquid chromatography (UPLC) coupled to quadrupole-time of flight mass spectrometry is presented. Pressurized liquid extraction (PLE) was also tested as extraction technique but it was discarded because cynarin was not stable under temperature values used in PLE. The separation of the CQAs isomers was carried out in only seven minutes. FUSLE variables such as extraction solvent, power and time were optimized by a central composite design. Under optimal conditions, FUSLE extraction was performed with 8mL of an 83:17 methanol-water mixture for 30s at a power of 60%. Only two extraction steps were found necessary to recover analytes quantitatively. Sensitivity, linearity, accuracy and precision were established. Matrix effect was studied for each type of sample. It was not detected for mono-CQAs, whereas the cynarin signal was strongly decreased due to ionization suppression in presence of matrix components; so the quantification by standard addition was mandatory for the determination of di-caffeoylquinic acids. Finally, the method was applied to the analysis of herbal extracts, feed additives and finished feed. In all samples, chlorogenic acid was the predominant CQA, followed by criptochlorogenic acid, neochlorogenic acid and cynarin. The method allows an efficient determination of chlorogenic acid with good recovery rates. Therefore, it may be used for screening of raw material and for process and quality control in feed manufacture. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Multiresidue analysis of 47 pesticides in cooked wheat flour and polished rice by liquid chromatography with tandem mass spectrometry.

    PubMed

    Lee, Sung Jung; Park, Hyeong Jin; Kim, Wooseong; Jin, Jong Sung; Abd El-Aty, A M; Shim, Jae-Han; Shin, Sung Chul

    2009-04-01

    Liquid chromatography in conjunction with tandem mass spectrometry was used to directly quantify of 47 pesticide residues from cooked wheat flour and polished rice, which are the most widely consumed cereals in the Republic of Korea. The sample clean-up was carried out according to the method established by the Korea Food and Drug Administration. The mobile phase for liquid chromatography separation consisted of water and 5 mm methanolic ammonium formate. Tandem mass spectroscopy experiments were performed in electrospray ionization positive mode and the multiple reaction monitoring mode. The matrix effects estimated for the 47 pesticides had a mean value of 99% and ranged from 45 to 147%. High recoveries (70-140%) and relative standard deviations (< or = 20%) were achieved for most of the pesticides tested. The method used in this study allowed for rapid quantification and identification of low levels of pesticides in cooked wheat flour and polished rice samples. Of the screened pesticide residues, only tricyclazole and fenobucarb were found in polished rice samples. However, no samples contained residues above the MRL established by the Korea Food and Drug Administration.

  13. A simple dual online ultra-high pressure liquid chromatography system (sDO-UHPLC) for high throughput proteome analysis.

    PubMed

    Lee, Hangyeore; Mun, Dong-Gi; Bae, Jingi; Kim, Hokeun; Oh, Se Yeon; Park, Young Soo; Lee, Jae-Hyuk; Lee, Sang-Won

    2015-08-21

    We report a new and simple design of a fully automated dual-online ultra-high pressure liquid chromatography system. The system employs only two nano-volume switching valves (a two-position four port valve and a two-position ten port valve) that direct solvent flows from two binary nano-pumps for parallel operation of two analytical columns and two solid phase extraction (SPE) columns. Despite the simple design, the sDO-UHPLC offers many advantageous features that include high duty cycle, back flushing sample injection for fast and narrow zone sample injection, online desalting, high separation resolution and high intra/inter-column reproducibility. This system was applied to analyze proteome samples not only in high throughput deep proteome profiling experiments but also in high throughput MRM experiments.

  14. A bioequivalence study of gliclazide based on quantification by high-performance liquid chromatography coupled with electrospray tandem mass spectrometry.

    PubMed

    Mendes, G D; Moreira, L D; Pereira, A dos S; Borges, A; Yui, F; Mendes, F D; de Nucci, G

    2007-03-01

    The aim of this study was to evaluate, in human volunteers, the performance of one gliclazide tablet formulation (gliclazide 80 mg tablet from EMS Indústria Farmacêutica Ltda.) against two reference gliclazide tablet formulations (Diamicron 80 mg tablet from Servier do Brazil Ltda. and Diamicron 80 mg tablet from Servier (Ireland) Industries Limited). The study had an open, randomized, three-period crossover design with a one-week washout interval between doses. The samples were obtained over a 48-h interval after each oral administration of gliclazide. The samples were extracted from plasma using diethylether : hexane (80 : 20, v/v) and the extracts were analyzed by high-performance liquid chromatography coupled with electrospray tandem mass spectrometry (HPLC-MS/ MS). Chromatography was performed isocratically using a Jones Chromatography Genesis C8 120A 4u. The method had a chromatographic run-time of 2.5 min and a calibration curve of the range of 0.02- 10 microg x ml(-1) (r(2) > 0.9993). The limit of quantification was 0.02 microg x ml(-1). The geometric mean and 90% confidence intervals (CI) for the Gliclazide/Diamicron (Ireland) ratio were 588.68% (90% CI= 491.16, 705.58%) for AUClast, 423.50% (90% CI = 338.25, 530.23%) for AUCinf, and 1395.77% (90% CI= 1116.62, 1744.72%) for Cmax. The geometric mean and 90% confidence intervals (CI) for the Gliclazide/Diamicron (Brazil) ratio were 249.16% (90% CI = 207.96, 298.54%) for AUCiast, 249.16% (90% CI = 207.96 - 298.54%) for AUCinf, and 188.04% (90% CI - 151.72, 233.05%) for Cmax. Since the 90% CI for Cmax, AUClast and AUC(0-infinity) ratios were all outside the 125% interval proposed by the US Food and Drug Administration, we concluded that the gliclazide test formulation were not bioequivalent to either reference formulation. Interestingly, the pharmacokinetic parameters such as Cmax, AUClast of both reference formulations are compatible with neither the literature nor the profile of an immediate release

  15. Simultaneous determination of ambroxol and salbutamol in human plasma by ultra-performance liquid chromatography-tandem mass spectrometry and its application to a pharmacokinetic study.

    PubMed

    Guo, Zhening; Chen, Yangsheng; Ding, Xiaoliang; Huang, Chenrong; Miao, Liyan

    2016-11-01

    A rapid, selective and sensitive liquid chromatography-tandem mass spectrometry assay method was developed for simultaneous determination of ambroxol and salbutamol in human plasma using citalopram hydrobromide as internal standard (IS). The sample was alkalinized with ammonia water (33:67, v/v) and extracted by single liquid-liquid extraction with ethyl acetate. Separation was achieved on Waters Acquity UPLC BEH C 18 column using a gradient program at a flow rate of 0.2 mL/min. Detection was performed using electrospray ionization in positive ion multiple reaction monitoring mode by monitoring the ion transitions m/z 378.9 → 263.6 (ambroxol), m/z 240.2 → 147.7 (salbutamol) and m/z 325.0 → 261.7 (IS). The total analytical run time was relatively short (3 min). Calibration curves were linear in the concentration range of 0.5-100.0 ng/mL for ambroxol and 0.2-20.0 ng/mL for salbutamol, with intra- and inter-run precision (relative standard deviation) <15% and accuracy (relative error) ranging from 97.7 to 112.1% for ambroxol and from 94.5 to 104.1% for salbutamol. The method was successfully applied in a clinical pharmacokinetic study of the compound ambroxol and salbutamol tablets. Copyright © 2016 John Wiley & Sons, Ltd.

  16. Quantification of Tea Flavonoids by High Performance Liquid Chromatography

    ERIC Educational Resources Information Center

    Freeman, Jessica D.; Niemeyer, Emily D.

    2008-01-01

    We have developed a laboratory experiment that uses high performance liquid chromatography (HPLC) to quantify flavonoid levels in a variety of commercial teas. Specifically, this experiment analyzes a group of flavonoids known as catechins, plant-derived polyphenolic compounds commonly found in many foods and beverages, including green and black…

  17. Ultra trace determination of 31 pesticides in water samples by direct injection-rapid resolution liquid chromatography-electrospray tandem mass spectrometry.

    PubMed

    Díaz, Laura; Llorca-Pórcel, Julio; Valor, Ignacio

    2008-08-22

    A liquid chromatography-tandem mass spectrometry (LC-MS/MS)-based method for the detection of pesticides in tap and treated wastewater was developed and validated according to the ISO/IEC 17025:1999. Key features of this method include direct injection of 100 microL of sample, an 11 min separation by means of a rapid resolution liquid chromatography system with a 4.6 mm x 50 mm, 1.8 microm particle size reverse phase column and detection by electrospray ionization (ESI) MS-MS. The limits of detection were below 15 ng L(-1) and correlation coefficients for the calibration curves in the range of 30-2000 ng L(-1) were higher than 0.99. Precision was always below 20% and accuracy was confirmed by external evaluation. The main advantages of this method are direct injection of sample without preparative procedures and low limits of detection that fulfill the requirements established by the current European regulations governing pesticide detection.

  18. An ultra-pressure liquid chromatography-tandem mass spectrometry method for the simultaneous determination of three physalins in rat plasma and its application to pharmacokinetic study of Physalis alkekengi var. franchetii (Chinese lantern) in rats.

    PubMed

    Zheng, Yunliang; Chen, Yong; Ren, Yiping; Luan, Lianjun; Wu, Yongjiang

    2012-01-25

    An ultra-high pressure liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was developed for the quantification of three major ingredients in Chinese lantern preparations (CLP) in rat plasma. Following extraction by ethyl acetate, the analytes were separated on an Acquity UPLC BEH Shield RP C(18) column using a gradient mobile phase system of acetonitrile-water. Electrospray ionization (ESI) tandem interface was employed prior to mass spectrometric detection. The calibration curves were linear over the range of 5.0-500.0 ng/ml for physalin D, 2.3-230.0 ng/ml for physalin G and 0.71-71.0 ng/ml for 4,7-didehydroneophysalin B. The average extraction recoveries, examined at four concentration levels, carried from 57.1% to 76.9%, and the accuracies ranged from 94.0% to 113.3% with precision (RSD) <15%. The validated method was successfully applied to the determination of the three physalins in rat plasma after intragastric administration of CLP suspension. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. High-resolution liquid chromatography/electrospray ionization time-of-flight mass spectrometry combined with liquid chromatography/electrospray ionization tandem mass spectrometry to identify polyphenols from grape antioxidant dietary fiber.

    PubMed

    Touriño, Sonia; Fuguet, Elisabet; Jáuregui, Olga; Saura-Calixto, Fulgencio; Cascante, Marta; Torres, Josep Lluís

    2008-11-01

    Grape antioxidant dietary fiber (GADF) is a dietary supplement that combines the benefits of both fiber and antioxidants that help prevent cancer and cardiovascular diseases. The antioxidant polyphenolic components in GADF probably help prevent cancer in the digestive tract, where they are bioavailable. Mass spectrometry coupled to liquid chromatography is a powerful tool for the analysis of complex plant derivatives such as GADF. We use a combination of MS techniques, namely liquid chromatography/electrospray ionization time-of-flight mass spectrometry (LC/ESI-TOF-MS) and liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) on a triple quadrupole, for the identification of the polyphenolic constituents of the soluble fraction of GADF. First, we separated the mixture into four fractions which were tested for phenolic constituents using the TOF system in the full scan mode. The high sensitivity and resolution of the TOF detector over the triple quadrupole facilitate the preliminary characterization of the fractions. Then we used LC/ESI-MS/MS to identify the individual phenols through MS/MS experiments (product ion scan, neutral loss scan, precursor ion scan). Finally, most of the identities were unequivocally confirmed by accurate mass measurements on the TOF spectrometer. LC/ESI-TOF-MS combined with MS/MS correctly identifies the bioactive polyphenolic components from the soluble fraction of GADF. High-resolution TOF-MS is particularly useful for identifying the structure of compounds with the same LC/ESI-MS/MS fragmentation patterns.

  20. Quantitation of five organophosphorus nerve agent metabolites in serum using hydrophilic interaction liquid chromatography and tandem mass spectrometry

    PubMed Central

    Hamelin, Elizabeth I.; Schulze, Nicholas D.; Shaner, Rebecca L.; Coleman, Rebecca M.; Lawrence, Richard J.; Crow, Brian S.; Jakubowski, E. M.; Johnson, Rudolph C.

    2015-01-01

    Although nerve agent use is prohibited, concerns remain for human exposure to nerve agents during decommissioning, research, and warfare. Exposure can be detected through the analysis of the hydrolysis products in urine as well as blood. An analytical method to detect exposure to five nerve agents, including VX, VR (Russian VX), GB (sarin), GD (soman) and GF (cyclosarin), through the analysis of the hydrolysis products, which are the primary metabolites, in serum has been developed and characterized. This method uses solid phase extraction coupled with high performance liquid chromatography for separation and isotopic dilution tandem mass spectrometry for detection. An uncommon buffer of ammonium fluoride was used to enhance ionization and improve sensitivity when coupled with hydrophilic interaction liquid chromatography resulting in detection limits from 0.3–0.5 ng/mL. The assessment of two quality control samples demonstrated high accuracy (101–105%) and high precision (5–8%) for the detection of these five nerve agent hydrolysis products in serum. PMID:24633507

  1. Development of an ultra-high-pressure liquid chromatography-tandem mass spectrometry multi-residue sulfonamide method and its application to water, manure slurry, and soils from swine rearing facilities.

    PubMed

    Shelver, Weilin L; Hakk, Heldur; Larsen, Gerald L; DeSutter, Thomas M; Casey, Francis X M

    2010-02-19

    An analytical method was developed using ultra-high-pressure liquid chromatography-triple quadrupole-tandem mass spectrometry (UHPLC-TQ-MS/MS) to simultaneously analyze 14 sulfonamides (SA) in 6 min. Despite the rapidity of the assay the system was properly re-equilibrated in this time. No carryover was observed even after high analyte concentrations. The instrumental detection limit based on signal-to-noise ratio (S/N)>3, was below 1 pg/microL (5 pg on column) for all SAs except sulfachloropyridazine. Surface water, ground water, soil, and slurry manure contained in storage ponds in and around swine [Sus scrofa domesticus] rearing facilities were analyzed. Sample cleanup for ground water and surface water included using solid phase extraction (SPE) using Oasis hydrophilic-lipophilic balance (HLB) cartridges. The soil and slurry manure required tandem strong anion exchange (SAX) and HLB solid phase extraction cartridges for sample cleanup. With few exceptions, the recoveries ranged from 60 to 100% for all matrices. The minimum detectable levels were below 2.0 ng/L for water, 30 ng/L for slurry manure, and 45 ng/kg for soil except for sulfachloropyridazine. The coefficient of variation (CV) was within 20% for most of the compounds analyzed. Using this method, sulfamethazine concentrations of 2250-5060 ng/L, sulfamethoxazole concentrations of 108-1.47 x 10(6)ng/L, and sulfathiazole concentrations of 785-1700 ng/L were found in the slurry manure. Sulfadimethoxine (2.0-32 ng/L), sulfamethazine (2.0-5.1 ng/L), and sulfamethoxazole (20.5-43.0 ng/L) were found in surface water and ground water. In top soil (0-15 cm), sulfamethazine ranged 34.5-663 ng/kg dry weight in those locations that received slurry manure as a nutrient; no SAs were found in the soil depths between 46 and 61 cm. The speed makes the method practical for medium to high throughput applications. The sensitivity and positive analyte identification make the method suitable for the demanding requirements for

  2. Histamine and tele-methylhistamine quantification in cerebrospinal fluid from narcoleptic subjects by liquid chromatography tandem mass spectrometry with precolumn derivatization.

    PubMed

    Croyal, Mikaël; Dauvilliers, Yves; Labeeuw, Olivier; Capet, Marc; Schwartz, Jean-Charles; Robert, Philippe

    2011-02-01

    An ultra-performance liquid chromatography tandem mass spectrometry (UPLC™-MS/MS) assay was developed for the simultaneous analysis of histamine, its major metabolite tele-methylhistamine, and an internal standard (N-tele-(R)-α-dimethylhistamine) from human cerebrospinal fluid (CSF) samples. The method involves derivatization of primary amines with 4-bromobenzenesulfonyl chloride and subsequent analysis by reversed phase liquid chromatography with mass spectrometry detection and positive electrospray ionization. The separation of derivatized biogenic amines was achieved within 3.5 min on an Acquity® BEH C(18) column by elution with a linear gradient of acetonitrile/water/formic acid (0.1%). The assay was linear in the concentration range of 50-5000 pM for each amine (5.5-555 pg/ml for histamine and 6.25-625 pg/ml for tele-methylhistamine). For repeatability and precision determination, coefficients of variation (CVs) were less than 11.0% over the tested concentration ranges, within acceptance criteria. Thus, the developed method provides the rapid, easy, highly sensitive, and selective requirement to quantify these amines in human CSF. No significant difference was found in the mean ± standard error levels of these amines between a group of narcoleptic patients (histamine=392 ± 64 pM, tele-methylhistamine=2431 ± 461 pM, n=7) and of neurological control subjects (histamine=402 ± 72 pM, tele-methylhistamine=2209 ± 463 pM, n=32). Copyright © 2010 Elsevier Inc. All rights reserved.

  3. Simultaneous determination of mushroom toxins α-amanitin, β-amanitin and muscarine in human urine by solid-phase extraction and ultra-high-performance liquid chromatography coupled with ultra-high-resolution TOF mass spectrometry.

    PubMed

    Tomková, Jana; Ondra, Peter; Válka, Ivo

    2015-06-01

    This paper presents a method for the simultaneous determination of α-amanitin, β-amanitin and muscarine in human urine by solid-phase extraction (SPE) and ultra-high-performance liquid chromatography coupled with ultra-high-resolution TOF mass spectrometry. The method can be used for a diagnostics of mushroom poisonings. Different SPE cartridges were tested for sample preparation, namely hydrophilic modified reversed-phase (Oasis HLB) and polymeric weak cation phase (Strata X-CW). The latter gave better results and therefore it was chosen for the subsequent method optimization and partial validation. In the course of validation, limits of detection, linearity, intraday and interday precisions and recoveries were evaluated. The obtained LOD values of α-amanitin and β-amanitin were 1ng/mL and of muscarine 0.09ng/mL. The intraday and interday precisions of human urine spiked with α-amanitin (10ng/mL), β-amanitin (10ng/mL) and muscarine (1ng/mL) ranged from 6% to 10% and from 7% to 13%, respectively. The developed method was proved to be a relevant tool for the simultaneous determination of the studied mushroom toxins in human urine after mushroom poisoning. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  4. [Determination of four bisphenolic compounds in drinking water by liquid chromatography-tandem mass spectrometry].

    PubMed

    Hu, Xiaojian; Zhang, Haijing; Wang, Xiaohong; Ding, Changming; Lin, Shaobin

    2015-05-01

    To simultaneously determine the four bisphenolic compounds (bisphenol F, bisphenol A, tetrachlorobisphenol A and tetrabromobisphenol A) in drinking water by liquid chromatography tandem mass spectrometry. 200 ml water sample was extracted by solid-phase extraction, eluted with methanol and analyzed by liquid chromatography tandem mass spectrometry under the MRM mode. The separation was carried out on a T3 column (2.1 mm x 150 mm, 3 μm). The limits of detection for the four bisphenolic compounds were in the range of 0.20 - 5.5 ng/L. The mean recoveries at the two spiked levels were 87.1% - 109.0% with the intra-day precision between 6.3% - 12.4% and inter-day precision between 4.5% - 15.4%. The method was applied for determination of 15 water samples. The method was sensitive, precise and accurate.

  5. Quantification of methionine and selenomethionine in biological samples using multiple reaction monitoring high performance liquid chromatography tandem mass spectrometry (MRM-HPLC-MS/MS).

    PubMed

    Vu, Dai Long; Ranglová, Karolína; Hájek, Jan; Hrouzek, Pavel

    2018-05-01

    Quantification of selenated amino-acids currently relies on methods employing inductively coupled plasma mass spectrometry (ICP-MS). Although very accurate, these methods do not allow the simultaneous determination of standard amino-acids, hampering the comparison of the content of selenated versus non-selenated species such as methionine (Met) and selenomethionine (SeMet). This paper reports two approaches for the simultaneous quantification of Met and SeMet. In the first approach, standard enzymatic hydrolysis employing Protease XIV was applied for the preparation of samples. The second approach utilized methanesulfonic acid (MA) for the hydrolysis of samples, either in a reflux system or in a microwave oven, followed by derivatization with diethyl ethoxymethylenemalonate. The prepared samples were then analyzed by multiple reaction monitoring high performance liquid chromatography tandem mass spectrometry (MRM-HPLC-MS/MS). Both approaches provided platforms for the accurate determination of selenium/sulfur substitution rate in Met. Moreover the second approach also provided accurate simultaneous quantification of Met and SeMet with a low limit of detection, low limit of quantification and wide linearity range, comparable to the commonly used gas chromatography mass spectrometry (GC-MS) method or ICP-MS. The novel method was validated using certified reference material in conjunction with the GC-MS reference method. Copyright © 2018. Published by Elsevier B.V.

  6. Serum metabolic profiling study of lung cancer using ultra high performance liquid chromatography/quadrupole time-of-flight mass spectrometry.

    PubMed

    Li, Yanjie; Song, Xue; Zhao, Xinjie; Zou, Lijuan; Xu, Guowang

    2014-09-01

    Lung cancer is currently the leading cause of cancer-related mortality worldwide. It is, therefore, important to enhance understanding and add a new auxiliary detection tool of lung cancer. In this work, serum metabolic characteristics of lung cancer were investigated with a non-targeted metabolomics method. The metabolic profiling of 23 patients with lung cancer and 23 healthy controls were analyzed using ultra high performance liquid chromatography/quadrupole time of flight mass spectrometry (UPLC/Q-TOF MS). Partial least squares discriminant analysis (PLS-DA) model of the metabolic data allowed the clear separation of the lung cancer patients from the healthy controls. In total, 27 differential metabolites were identified, which were mostly related to the perturbation of lipid metabolism, including choline, free fatty acids, lysophosphatidylcholines, etc. Choline and linoleic acid were defined as one combinational biomarker using binary logistic regression, which was supported by the validation with a smaller sample-set (9 patients and 9 healthy controls). These findings show that LC/MS-based serum metabolic profiling has potential application in complementary identification of lung cancer patients, and could be a powerful tool for cancer research. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Highly informative multiclass profiling of lipids by ultra-high performance liquid chromatography - Low resolution (quadrupole) mass spectrometry by using electrospray ionization and atmospheric pressure chemical ionization interfaces.

    PubMed

    Beccaria, Marco; Inferrera, Veronica; Rigano, Francesca; Gorynski, Krzysztof; Purcaro, Giorgia; Pawliszyn, Janusz; Dugo, Paola; Mondello, Luigi

    2017-08-04

    A simple, fast, and versatile method, using an ultra-high performance liquid chromatography system coupled with a low resolution (single quadrupole) mass spectrometer was optimized to perform multiclass lipid profiling of human plasma. Particular attention was made to develop a method suitable for both electrospray ionization and atmospheric pressure chemical ionization interfaces (sequentially in positive- and negative-ion mode), without any modification of the chromatographic conditions (mobile phase, flow-rate, gradient, etc.). Emphasis was given to the extrapolation of the structural information based on the fragmentation pattern obtained using atmospheric pressure chemical ionization interface, under each different ionization condition, highlighting the complementary information obtained using the electrospray ionization interface, of support for related molecule ions identification. Furthermore, mass spectra of phosphatidylserine and phosphatidylinositol obtained using the atmospheric pressure chemical ionization interface are reported and discussed for the first time. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. High-Performance Liquid Chromatography in the Undergraduate Chemical Engineering Laboratory

    ERIC Educational Resources Information Center

    Frey, Douglas D.; Guo, Hui; Karnik, Nikhila

    2013-01-01

    This article describes the assembly of a simple, low-cost, high-performance liquid chromatography (HPLC) system and its use in the undergraduate chemical engineering laboratory course to perform simple experiments. By interpreting the results from these experiments students are able to gain significant experience in the general method of…

  9. Simultaneous determination of chromones and coumarins in Radix Saposhnikoviae by high performance liquid chromatography with diode array and tandem mass detectors.

    PubMed

    Kim, Min Kyung; Yang, Dong-Hyug; Jung, Mihye; Jung, Eun Ha; Eom, Han Young; Suh, Joon Hyuk; Min, Jung Won; Kim, Unyong; Min, Hyeyoung; Kim, Jinwoong; Han, Sang Beom

    2011-09-16

    Methods using high performance liquid chromatography with diode array detection (HPLC-DAD) and tandem mass spectrometry (HPLC-MS/MS) were developed and validated for the simultaneous determination of 5 chromones and 6 coumarins: prim-O-glucosylcimifugin (1), cimifugin (2), nodakenin (3), 4'-O-β-d-glucosyl-5-O-methylvisamminol (4), sec-O-glucosylhamaudol (5), psoralen (6), bergapten (7), imperatorin (8), phellopterin (9), 3'-O-angeloylhamaudol (10) and anomalin (11), in Radix Saposhnikoviae. The separation conditions for HPLC-DAD were optimized using an Ascentis Express C18 (4.6 mm×100 mm, 2.7 μm particle size) fused-core column. The mobile phase was composed of 10% aqueous acetonitrile (A) and 90% acetonitrile (B) and the elution was performed under a gradient mode at a flow rate of 1.0 mL/min. The detection wavelength was set at 300 nm. The HPLC-DAD method yielded a base line separation of the 11 components in 50% methanol extract of Radix Saposhnikoviae with no interfering peaks detected. The HPLC-DAD method was validated in terms of linearity, accuracy and precision (intra- and inter-day), limit of quantification (LOQ), recovery, and robustness. Specific determination of the 11 components was also accomplished by a triple quadrupole tandem mass spectrometer equipped with an electrospray ionization (ESI) source. This HPLC-MS/MS method was also validated by determining the linearity, limit of quantification, accuracy, and precision. Quantification of the 11 components in 51 commercial Radix Saposhnikoviae samples was successfully performed using the developed HPLC-DAD method. The identity, batch-to-batch consistency, and authenticity of Radix Saposhnikoviae were successfully monitored by the proposed HPLC-DAD and HPLC-MS/MS methods. Copyright © 2011 Elsevier B.V. All rights reserved.

  10. High Performance Thin Layer Chromatography.

    ERIC Educational Resources Information Center

    Costanzo, Samuel J.

    1984-01-01

    Clarifies where in the scheme of modern chromatography high performance thin layer chromatography (TLC) fits and why in some situations it is a viable alternative to gas and high performance liquid chromatography. New TLC plates, sample applications, plate development, and instrumental techniques are considered. (JN)

  11. [Screening and confirmation of 24 hormones in cosmetics by ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry].

    PubMed

    Li, Zhaoyong; Wang, Fengmei; Niu, Zengyuan; Luo, Xin; Zhang, Gang; Chen, Junhui

    2014-05-01

    A method of ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry (UPLC-LTQ/Orbitrap MS) was established to screen and confirm 24 hormones in cosmetics. Various cosmetic samples were extracted with methanol. The extract was loaded onto a Waters ACQUITY UPLC BEH C18 column (50 mm x 2.1 mm, 1.7 microm) using a gradient elution of acetonitrile/water containing 0.1% (v/v) formic acid for the separation. The accurate mass of quasi-molecular ion was acquired by full scanning of electrostatic field orbitrap. The rapid screening was carried out by the accurate mass of quasi-molecular ion. The confirmation analysis for targeted compounds was performed with the retention time and qualitative fragments obtained by data dependent scan mode. Under the optimal conditions, the 24 hormones were routinely detected with mass accuracy error below 3 x 10(-6) (3 ppm), and good linearities were obtained in their respective linear ranges with correlation coefficients higher than 0.99. The LODs (S/N = 3) of the 24 compounds were < or = 10 microg/kg, which can meet the requirements for the actual screening of cosmetic samples. The developed method was applied to screen the hormones in 50 cosmetic samples. The results demonstrate that the method is a useful tool for the rapid screening and identification of the hormones in cosmetics.

  12. Quantitative determination of multi markers in five varieties of Withania somnifera using ultra-high performance liquid chromatography with hybrid triple quadrupole linear ion trap mass spectrometer combined with multivariate analysis: Application to pharmaceutical dosage forms.

    PubMed

    Chandra, Preeti; Kannujia, Rekha; Saxena, Ankita; Srivastava, Mukesh; Bahadur, Lal; Pal, Mahesh; Singh, Bhim Pratap; Kumar Ojha, Sanjeev; Kumar, Brijesh

    2016-09-10

    An ultra-high performance liquid chromatography electrospray ionization tandem mass spectrometry method has been developed and validated for simultaneous quantification of six major bioactive compounds in five varieties of Withania somnifera in various plant parts (leaf, stem and root). The analysis was accomplished on Waters ACQUITY UPLC BEH C18 column with linear gradient elution of water/formic acid (0.1%) and acetonitrile at a flow rate of 0.3mLmin(-1). The proposed method was validated with acceptable linearity (r(2), 0.9989-0.9998), precision (RSD, 0.16-2.01%), stability (RSD, 1.04-1.62%) and recovery (RSD ≤2.45%), under optimum conditions. The method was also successfully applied for the simultaneous determination of six marker compounds in twenty-six marketed formulations. Hierarchical cluster analysis and principal component analysis were applied to discriminate these twenty-six batches based on characteristics of the bioactive compounds. The results indicated that this method is advance, rapid, sensitive and suitable to reveal the quality of Withania somnifera and also capable of performing quality evaluation of polyherbal formulations having similar markers/raw herbs. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Determination of virginiamycin M1 residue in tissues of swine and chicken by ultra-performance liquid chromatography tandem mass spectrometry.

    PubMed

    Wang, Xiaoyang; Wang, Mi; Zhang, Keyu; Hou, Ting; Zhang, Lifang; Fei, Chenzong; Xue, Feiqun; Hang, Taijun

    2018-06-01

    A reliable UPLC-MS/MS method with high sensitivity was developed and validated for the determination of virginiamycin M1 in muscle, fat, liver, and kidney samples of chicken and swine. Analytes were extracted using acetonitrile and extracts were defatted by N-hexane. Chromatographic separation was performed on a BEH C18 liquid chromatography column. The analytes were then detected using triplequadrupole mass spectrometry in positive electrospray ionization and multiple reaction monitoring mode. Calibration plots were constructed using standard working solutions and showed good linearity. Limits of quantification ranged from 2 to 60 ng mL -1 . Copyright © 2018 Elsevier Ltd. All rights reserved.

  14. Determination of Caffeine in Beverages by High Performance Liquid Chromatography.

    ERIC Educational Resources Information Center

    DiNunzio, James E.

    1985-01-01

    Describes the equipment, procedures, and results for the determination of caffeine in beverages by high performance liquid chromatography. The method is simple, fast, accurate, and, because sample preparation is minimal, it is well suited for use in a teaching laboratory. (JN)

  15. Concentration determination of urinary metabolites of N,N-dimethylacetamide by high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Yamamoto, Shinobu; Matsumoto, Akiko; Yui, Yuko; Miyazaki, Shota; Kumagai, Shinji; Hori, Hajime; Ichiba, Masayoshi

    2018-03-27

    N,N-Dimethylacetamide (DMAC) is widely used in industry as a solvent. It can be absorbed through human skin. Therefore, it is necessary to determine exposure to DMAC via biological monitoring. However, the precision of traditional gas chromatography (GC) is low due to the thermal decomposition of metabolites in the high-temperature GC injection port. To overcome this problem, we have developed a new method for the simultaneous separation and quantification of urinary DMAC metabolites using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Urine samples were diluted 10-fold in formic acid, and 1-μl aliquots were injected into the LC-MS/MS equipment. A C18 reverse-phase Octa Decyl Silyl (ODS) column was used as the analytical column, and the mobile phase consisted of a mixture of methanol and aqueous formic acid solution. Urinary concentrations of DMAC and its known metabolites (N-hydroxymethyl-N-methylacetamide (DMAC-OH), N-methylacetamide (NMAC), and S- (acetamidomethyl) mercapturic acid (AMMA) ) were determined in a single run. The dynamic ranges of the calibration curves were 0.05-5 mg/l (r≥0.999) for all four compounds. The limits of detection for DMAC, DMAC-OH, NMAC, and AMMA in urine were 0.04, 0.02, 0.05, and 0.02 mg/l, respectively. Within-run accuracies were 96.5%-109.6% with relative standard deviations of precision being 3.43%-10.31%. The results demonstrated that the proposed method could successfully quantify low concentrations of DMAC and its metabolites with high precision. Hence, this method is useful for evaluating DMAC exposure. In addition, this method can be used to examine metabolite behaviors in human bodies after exposure and to select appropriate biomarkers.

  16. Concentration determination of urinary metabolites of N,N-dimethylacetamide by high-performance liquid chromatography-tandem mass spectrometry

    PubMed Central

    Yamamoto, Shinobu; Matsumoto, Akiko; Yui, Yuko; Miyazaki, Shota; Kumagai, Shinji; Hori, Hajime; Ichiba, Masayoshi

    2017-01-01

    Objectives: N,N-Dimethylacetamide (DMAC) is widely used in industry as a solvent. It can be absorbed through human skin. Therefore, it is necessary to determine exposure to DMAC via biological monitoring. However, the precision of traditional gas chromatography (GC) is low due to the thermal decomposition of metabolites in the high-temperature GC injection port. To overcome this problem, we have developed a new method for the simultaneous separation and quantification of urinary DMAC metabolites using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Methods: Urine samples were diluted 10-fold in formic acid, and 1-μl aliquots were injected into the LC-MS/MS equipment. A C18 reverse-phase Octa Decyl Silyl (ODS) column was used as the analytical column, and the mobile phase consisted of a mixture of methanol and aqueous formic acid solution. Results: Urinary concentrations of DMAC and its known metabolites (N-hydroxymethyl-N-methylacetamide (DMAC-OH), N-methylacetamide (NMAC), and S- (acetamidomethyl) mercapturic acid (AMMA) ) were determined in a single run. The dynamic ranges of the calibration curves were 0.05-5 mg/l (r≥0.999) for all four compounds. The limits of detection for DMAC, DMAC-OH, NMAC, and AMMA in urine were 0.04, 0.02, 0.05, and 0.02 mg/l, respectively. Within-run accuracies were 96.5%-109.6% with relative standard deviations of precision being 3.43%-10.31%. Conclusions: The results demonstrated that the proposed method could successfully quantify low concentrations of DMAC and its metabolites with high precision. Hence, this method is useful for evaluating DMAC exposure. In addition, this method can be used to examine metabolite behaviors in human bodies after exposure and to select appropriate biomarkers. PMID:29213009

  17. Suitability of ultra-high performance liquid chromatography for the determination of fat-soluble nutritional status (vitamins A, E, D, and individual carotenoids).

    PubMed

    Granado-Lorencio, F; Herrero-Barbudo, C; Blanco-Navarro, I; Pérez-Sacristán, B

    2010-06-01

    Our aim was to assess the suitability of ultra-high performance liquid chromatography (UHPLC) for the simultaneous determination of biomarkers of vitamins A (retinol, retinyl esters), E (alpha- and gamma-tocopherol), D (25-OH-vitamin D), and the major carotenoids in human serum to be used in clinical practice. UHPLC analysis was performed on HSS T3 column (2.1 x 100 mm; 1.8 microm) using gradient elution and UV-VIS detection. The system allows the simultaneous determination of retinol, retinyl palmitate, 25-OH-vitamin D, alpha- and gamma-tocopherol, lutein plus zeaxanthin, alpha-carotene, beta-carotene, alpha- and beta-cryptoxanthin and lycopene. The method showed a good linearity over the physiological range with an adequate accuracy in samples from quality control programs. Suitability of the method in clinical practice was tested by analyzing samples (n = 286) from patients. In conclusion, UHPLC constitutes a reliable approach for nutrient/biomarker profiling allowing the rapid, simultaneous and low-cost determination of vitamins A, E, and D (including vitamers and ester forms) and the major carotenoids in clinical practice.

  18. MEASUREMENT OF OXIDATIVE STRESS PARAMETERS USING LIQUID CHROMATOGRAPHY - TANDEM MASS SPECTROSCOPY (LC-MS/MS)

    EPA Science Inventory

    What is the study?
    An invited review article. Measurement of oxidative stress parameters using liquid chromatography-tandem mass spectroscopy (LC-MS/MS)
    Why was it done?
    Although oxidative stress is frequently cited as a cause of various adverse biological eff...

  19. Analysis of microdialysate monoamines, including noradrenaline, dopamine and serotonin, using capillary ultra-high performance liquid chromatography and electrochemical detection.

    PubMed

    Ferry, Barbara; Gifu, Elena-Patricia; Sandu, Ioana; Denoroy, Luc; Parrot, Sandrine

    2014-03-01

    Electrochemical methods are very often used to detect catecholamine and indolamine neurotransmitters separated by conventional reverse-phase high performance liquid chromatography (HPLC). The present paper presents the development of a chromatographic method to detect monoamines present in low-volume brain dialysis samples using a capillary column filled with sub-2μm particles. Several parameters (repeatability, linearity, accuracy, limit of detection) for this new ultrahigh performance liquid chromatography (UHPLC) method with electrochemical detection were examined after optimization of the analytical conditions. Noradrenaline, adrenaline, serotonin, dopamine and its metabolite 3-methoxytyramine were separated in 1μL of injected sample volume; they were detected above concentrations of 0.5-1nmol/L, with 2.1-9.5% accuracy and intra-assay repeatability equal to or less than 6%. The final method was applied to very low volume dialysates from rat brain containing monoamine traces. The study demonstrates that capillary UHPLC with electrochemical detection is suitable for monitoring dialysate monoamines collected at high sampling rate. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Validation of an automated solid-phase extraction method for the analysis of 23 opioids, cocaine, and metabolites in urine with ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Ramírez Fernández, María del Mar; Van Durme, Filip; Wille, Sarah M R; di Fazio, Vincent; Kummer, Natalie; Samyn, Nele

    2014-06-01

    The aim of this work was to automate a sample preparation procedure extracting morphine, hydromorphone, oxymorphone, norcodeine, codeine, dihydrocodeine, oxycodone, 6-monoacetyl-morphine, hydrocodone, ethylmorphine, benzoylecgonine, cocaine, cocaethylene, tramadol, meperidine, pentazocine, fentanyl, norfentanyl, buprenorphine, norbuprenorphine, propoxyphene, methadone and 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine from urine samples. Samples were extracted by solid-phase extraction (SPE) with cation exchange cartridges using a TECAN Freedom Evo 100 base robotic system, including a hydrolysis step previous extraction when required. Block modules were carefully selected in order to use the same consumable material as in manual procedures to reduce cost and/or manual sample transfers. Moreover, the present configuration included pressure monitoring pipetting increasing pipetting accuracy and detecting sampling errors. The compounds were then separated in a chromatographic run of 9 min using a BEH Phenyl analytical column on a ultra-performance liquid chromatography-tandem mass spectrometry system. Optimization of the SPE was performed with different wash conditions and elution solvents. Intra- and inter-day relative standard deviations (RSDs) were within ±15% and bias was within ±15% for most of the compounds. Recovery was >69% (RSD < 11%) and matrix effects ranged from 1 to 26% when compensated with the internal standard. The limits of quantification ranged from 3 to 25 ng/mL depending on the compound. No cross-contamination in the automated SPE system was observed. The extracted samples were stable for 72 h in the autosampler (4°C). This method was applied to authentic samples (from forensic and toxicology cases) and to proficiency testing schemes containing cocaine, heroin, buprenorphine and methadone, offering fast and reliable results. Automation resulted in improved precision and accuracy, and a minimum operator intervention, leading to safer sample

  1. Simultaneous Quantification of Free and Glucuronidated Cannabinoids in Human Urine by Liquid Chromatography-Tandem Mass Spectrometry

    PubMed Central

    Scheidweiler, Karl B.; Desrosiers, Nathalie A.; Huestis, Marilyn A.

    2012-01-01

    Background Cannabis is the most commonly abused drug of abuse and is commonly quantified during urine drug testing. We conducted a controlled drug administration studies investigating efficacy of urinary cannabinoid glucuronide metabolites for documenting recency of cannabis intake and for determining stability of urinary cannabinoids. Methods A liquid chromatography tandem mass spectrometry method was developed and validated quantifying Δ9-tetrahydrocannabinol (THC), 11-hydroxy-THC (11-OH-THC), 11-nor-9-carboxy-THC (THCCOOH), cannabidiol, cannabinol, THC-glucuronide and THCCOOH-glucuronide in 0.5 ml human urine via supported-liquid extraction. Chromatography was performed on an Ultra Biphenyl column with a gradient of 10 mmol/l ammonium acetate, pH 6.15 and 15% methanol in acetonitrile at 0. 4ml/min. Analytes were monitored by positive and negative mode electrospray ionization and multiple reaction monitoring mass spectrometry. Results Linear ranges were 0.5–50 ng/ml for THC-glucuronide, 1–100 ng/ml for THCCOOH, 11-OH-THC and cannabidiol, 2–100 ng/ml for THC and cannabinol, and 5–500 ng/ml for THCCOOH-glucuronide (R2>0.99). Mean extraction efficiencies were 34–73% with analytical recovery (bias) 80.5–118.0% and total imprecision 3.0–10.2% coefficient of variation. Conclusion This method simultaneously quantifies urinary cannabinoids and phase II glucuronide metabolites, and enables evaluation of urinary cannabinoid glucuronides for documenting recency of cannabis intake and cannabinoid stability. The assay is applicable for routine urine cannabinoid testing. PMID:22771478

  2. An ultra performance liquid chromatography-tandem MS assay for tamoxifen metabolites profiling in plasma: first evidence of 4'-hydroxylated metabolites in breast cancer patients.

    PubMed

    Dahmane, E; Mercier, T; Zanolari, B; Cruchon, S; Guignard, N; Buclin, T; Leyvraz, S; Zaman, K; Csajka, C; Decosterd, L A

    2010-12-15

    There is increasing evidence that the clinical efficacy of tamoxifen, the first and most widely used targeted therapy for estrogen-sensitive breast cancer, depends on the formation of the active metabolites 4-hydroxy-tamoxifen and 4-hydroxy-N-desmethyl-tamoxifen (endoxifen). Large inter-individual variability in endoxifen plasma concentrations has been observed and related both to genetic and environmental (i.e. drug-induced) factors altering CYP450s metabolizing enzymes activity. In this context, we have developed an ultra performance liquid chromatography-tandem mass spectrometry method (UPLC-MS/MS) requiring 100 μL of plasma for the quantification of tamoxifen and three of its major metabolites in breast cancer patients. Plasma is purified by a combination of protein precipitation, evaporation at room temperature under nitrogen, and reconstitution in methanol/20 mM ammonium formate 1:1 (v/v), adjusted to pH 2.9 with formic acid. Reverse-phase chromatographic separation of tamoxifen, N-desmethyl-tamoxifen, 4-hydroxy-tamoxifen and 4-hydroxy-N-desmethyl-tamoxifen is performed within 13 min using elution with a gradient of 10 mM ammonium formate and acetonitrile, both containing 0.1% formic acid. Analytes quantification, using matrix-matched calibration samples spiked with their respective deuterated internal standards, is performed by electrospray ionization-triple quadrupole mass spectrometry using selected reaction monitoring detection in the positive mode. The method was validated according to FDA recommendations, including assessment of relative matrix effects variability, as well as tamoxifen and metabolites short-term stability in plasma and whole blood. The method is precise (inter-day CV%: 2.5-7.8%), accurate (-1.4 to +5.8%) and sensitive (lower limits of quantification comprised between 0.4 and 2.0 ng/mL). Application of this method to patients' samples has made possible the identification of two further metabolites, 4'-hydroxy-tamoxifen and 4'-hydroxy

  3. A liquid chromatography - tandem mass spectrometry method to measure a selected panel of uremic retention solutes derived from endogenous and colonic microbial metabolism.

    PubMed

    de Loor, Henriette; Poesen, Ruben; De Leger, Wout; Dehaen, Wim; Augustijns, Patrick; Evenepoel, Pieter; Meijers, Björn

    2016-09-14

    Chronic kidney disease (CKD) is associated with an increased risk of mortality and cardiovascular disease, which is, at least partly, mediated by the accumulation of so-called uremic retention solutes. Although there has been an increasing interest in the behavior of these solutes, derived from both the endogenous and colonic microbial metabolism, methods to simultaneously and accurately measure a broad panel of relevant uremic retention solutes remain scarce. We developed a highly sensitive ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method. A high throughput sample preparation was used with extraction of analytes from 50 μl serum using Ostro plate technology. For most solutes, stable isotopes labelled metabolites were used as internal standards. Chromatography was achieved using an Acquity UPLC CSH Fluoro Phenyl column. The total run time was 8 min, the mobile phase was a gradient of 0.1% formic acid in Milli-Q water and pure methanol at a flow rate of 0.5 ml min(-1). Detection was performed using a tandem mass spectrometer with alternated positive and negative electrospray ionization. Calibration curves were linear for all solutes. Precision was assessed according to the NCCLS EP5-T guideline, being below 15% for all metabolites. Mean recoveries were between 83 and 104% for all metabolites. The validated method was successfully applied in a cohort of 488 patients with CKD. We developed and validated a sensitive and robust UPLC-MS/MS method for quantification of 15 uremic retention solutes derived from endogenous and colonic microbial metabolism. This method allows for studying the behavior and relevance of these solutes in patients with CKD. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Neutral Fragment Filtering for Rapid Identification of New Diester-Diterpenoid Alkaloids in Roots of Aconitum carmichaeli by Ultra-High-Pressure Liquid Chromatography Coupled with Linear Ion Trap-Orbitrap Mass Spectrometry

    PubMed Central

    Qiu, Xiao Hui; Yang, Yi Ming; Zhu, Da Yuan; Xu, Wen

    2012-01-01

    A rapid and effective method was developed for separation and identification of diester-diterpenoid alkaloids (DDA) in the roots of Aconitum carmichaeli by ultra-high-pressure liquid chromatography coupled with high resolution LTQ-Orbitrap tandem mass spectrometry (UHPLC-LTQ-Orbitrap-MSn). According to accurate mass measurement and the characteristic neutral loss filtering strategy, a total of 42 diester-diterpenoid alkaloids (DDA) were rapidly detected and characterized or tentatively identified. Meanwhile, the proposed fragmentation pathways and the major diagnostic fragment ions of aconitine, mesaconitine and hypaconitine were investigated to trace DDA derivatives in crude plant extracts. 23 potential new compounds were successfully screened and characterized in Aconitum carmichaeli, including 16 short chain fatty acyls DDA, 4 N-dealkyl DDA and several isomers of aconitine, mesaconitine and hypaconitine. PMID:23285005

  5. Determination of boldenone sulfoconjugate and related steroid sulfates in equine urine by high-performance liquid chromatography/tandem mass spectrometry.

    PubMed

    Weidolf, L O; Lee, E D; Henion, J D

    1988-03-01

    Sulfoconjugated anabolic steroids were separated by micro-bore high-performance liquid chromatography. The eluent was introduced into the atmospheric pressure ion source of the triple-quadrupole mass spectrometer via an ion spray liquid chromatograph/mass spectrometer interface operated in the negative ion mode. The limit of detection was 10 pg on-column by selected ion monitoring of the molecular ion and the response increased linearly over a concentration range of 2.4 orders of magnitude. Following work-up by a liquid-solid extraction procedure of equine urine samples, full-scan daughter ion spectra of boldenone sulfate could be obtained up to 17 days after a therapeutic dose of boldenone undecylenate to a horse.

  6. Determination of naltrexone and 6beta-naltrexol in human blood: comparison of high-performance liquid chromatography with spectrophotometric and tandem-mass-spectrometric detection.

    PubMed

    Brünen, Sonja; Krüger, Ralf; Finger, Susann; Korf, Felix; Kiefer, Falk; Wiedemann, Klaus; Lackner, Karl J; Hiemke, Christoph

    2010-02-01

    We present data for a comparison of a liquid-chromatographic method coupled with tandem mass spectrometry (LC-MS/MS) and a high-performance liquid-chromatographic method with column switching and UV spectrophotometric detection. The two methods were developed for determination of naltrexone and 6beta-naltrexol in blood serum or plasma aiming to be used for therapeutic drug monitoring to guide the treatment of patients with naltrexone. For the high-performance liquid chromatography (HPLC)/UV detection, online sample cleanup was conducted on Perfect Bond C(18) material with 2% (vol/vol) acetonitrile in deionized water. Drugs were separated on a C(18) column using 11.5% (vol/vol) acetonitrile and 0.4% (vol/vol) N,N,N,N-tetramethylethylenediamine within 20 min. LC-MS/MS used naltrexone-d (3) and 6beta-naltrexol-d (4) as internal standards. After protein precipitation, the chromatographic separation was performed on a C(18) column by applying a methanol gradient (5-100%, vol/vol) with 0.1% formic acid over 9.5 min. The HPLC/UV method was found to be linear for concentrations ranging from 2 to 100 ng/ml, with a regression correlation coefficient of r (2) > 0.998 for naltrexone and 6beta-naltrexol. The limit of quantification was 2 ng/ml for naltrexone and 6beta-naltrexol. For the LC-MS/MS method the calibration curves were linear (r(2) > 0.999) from 0.5 to 200 ng/ml for both substances, and the limit of quantification was 0.5 ng/ml. The concentrations measured by the two methods correlated significantly for both substances (r(2) > 0.967; p < 0.001). Both methods could be used for therapeutic drug monitoring. The HPLC/UV method was advantageous regarding automatization and costs, whereas LC-MS/MS was superior with regard to sensitivity.

  7. A green ionic liquid-based vortex-forced MSPD method for the simultaneous determination of 5-HMF and iridoid glycosides from Fructus Corni by ultra-high performance liquid chromatography.

    PubMed

    Du, Kunze; Li, Jin; Bai, Yun; An, Mingrui; Gao, Xiu-Mei; Chang, Yan-Xu

    2018-04-01

    A simple and green ionic liquid-based vortex-forced matrix solid phase dispersion (IL-VFMSPD) method was presented to simultaneously extract 5-hydroxymethyl furfurol (5-HMF) and iridoid glycosides in Fructus Corni by ultra-high performance liquid chromatography. Ionic liquid was used as a green elution reagent in vortex-forced MSPD process. A few parameters such as the type of ionic liquid, the type of sorbent, ratio of sample to sorbent, the concentration and volume of ionic liquid, grinding time and vortex time, were investigated in detail and an orthogonal design experiment was introduced to confirm the best conditions in this procedure. With the final optimized method, the recoveries of the target compounds in Fructus Corni were in the range of 95.2-103% (RSD<5.0%) and the method displayed a good linearity within the range of 0.8-200 μg mL -1 for morroniside, sweroside, loganin, cornuside and 1.2-300 μg mL -1 for 5-HMF. The limits of detection ranged from 0.02 to 0.08 μg mL -1 for all compounds. The results showed that the newly established method was efficiently applied to extract and determine iridoid glycosides and 5-HMF for quality control of Fructus Corni. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Application of dispersive solid-phase extraction and ultra-fast liquid chromatography-tandem quadrupole mass spectrometry in food additive residue analysis of red wine.

    PubMed

    Chen, Xiao-Hong; Zhao, Yong-Gang; Shen, Hao-Yu; Jin, Mi-Cong

    2012-11-09

    A novel and effective dispersive solid-phase extraction (dSPE) procedure with rapid magnetic separation using ethylenediamine-functionalized magnetic polymer as an adsorbent was developed. The new procedure had excellent clean-up ability for the selective removal of the matrix in red wine. An accurate, simple, and rapid analytical method using ultra-fast liquid chromatography-tandem quadrupole mass spectrometry (UFLC-MS/MS) for the simultaneous determination of nine food additives (i.e., acesulfame, saccharin, sodium cyclamate, aspartame, benzoic acid, sorbic acid, stevioside, dehydroacetic acid, and neotame) in red wine was also used and validated. Recoveries ranging from 78.5% to 99.2% with relative standard deviations ranging from 0.46% to 6.3% were obtained using the new method. All target compounds showed good linearities in the tested range with correlation coefficients (r) higher than 0.9993. The limits of quantification for the nine food additives were between 0.10 μg/L and 50.0 μg/L. The proposed dSPE-UFLC-MS/MS method was successfully applied in the food-safety risk monitoring of real red wine in Zhejiang Province, China. Crown Copyright © 2012. Published by Elsevier B.V. All rights reserved.

  9. Determination of parabens in serum by liquid chromatography-tandem mass spectrometry: Correlation with lipstick use.

    PubMed

    Tahan, Gabriella Padovani; Santos, Nayara de Kássia Souza; Albuquerque, Ana Carolina; Martins, Isarita

    2016-08-01

    Parabens are the most widely used preservative and are considered to be relatively safe compounds. However, studies have demonstrated that they may have estrogenic activity, and there is ongoing debate regarding the safety and potential cancer risk of using products containing these compounds. In the present work, liquid chromatography-tandem mass spectrometry was applied to determine methylparaben and propylparaben concentrations in serum, and the results were correlated with lipstick application. Samples were analyzed using liquid-liquid extraction, followed by liquid chromatography-tandem mass spectrometry. The validation results demonstrated the linearity of the method over a range of 1-20 ng/mL, in addition to the method's precision and accuracy. A statistically significant difference was demonstrated between serum parabens in women who used lipstick containing these substances compared with those not using this cosmetic (p = 0.0005 and 0.0016, respectively), and a strong association was observed between serum parabens and lipstick use (Spearman correlation = 0.7202). Copyright © 2016 Elsevier Inc. All rights reserved.

  10. Rapid Screening and Characterization of Acetylcholinesterase Inhibitors from Yinhuang Oral Liquid Using Ultrafiltration-liquid Chromatography-electrospray Ionization Tandem Mass Spectrometry

    PubMed Central

    Zhang, Haomin; Guo, Yinan; Meng, Lingwen; Sun, Hui; Yang, Yinping; Gao, Ying; Sun, Jiaming

    2018-01-01

    Background: At present, approximately 17–25 million people in the world suffer from Alzheimer's disease (AD). The most efficacious and acceptable therapeutic drug clinically are the acetylcholinesterase inhibitors (AChEIs). Yinhuang oral liquid is a Chinese medicine preparation which contains AChEIs according to the literatures. However, no strategy has been presented for rapid screening and identification of AChEIs from Yinhuang oral liquid. Objective: To develop a method for rapid screening and identification of AChEIs from Yinhuang oral liquid using ultrafiltration–liquid chromatography–electrospray ionization tandem mass spectrometry (UF-LC-ESI-MS/MS). Materials and Methods: In this study, UF incubation conditions such as enzyme concentration, incubation time, and incubation temperature were optimized so as to get better screening results. The AChEIs from Yinhuang oral liquid were identified by high-performance liquid chromatography-ESI-MS and the improved Ellman method was used for the AChE inhibitory activity test in vitro. Results: The results showed that Yinhuang oral liquid can inhibit the activity of AChE. We screened and identified seven compounds with potential AChE inhibitory activity from Yinhuang oral liquid, which provided experimental basis for the treatment and prevention of AD. Conclusion: The current technique was used to directly screen the active ingredients with acetylcholinesterase inhibition from complex traditional Chinese medicine, which was simple, rapid, accurate, and suitable for high-throughput screening of AChEI from complex systems. SUMMARY A UF-LC-ESI-MS/MS method for rapid screening and identification of AChEIs from Yinhuang oral liquid was developedSeven compounds were screened and identified with potential AChE inhibitory activity from Yinhuang oral liquidIt provided experimental basis of Yinhuang oral liquid for the treating and preventing AD. Abbreviations used: (AD): Alzheimer's disease; (UF

  11. Metabolic profile of esculin in rats by ultra high performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Wang, Yinan; Zhao, Min; Ou, Yingfu; Zeng, Bowen; Lou, Xinyu; Wang, Miao; Zhao, Chunjie

    2016-05-01

    Esculin, a coumarin derivative found in Fraxinus rhynchophylla, has been reported to possess multiple biological activities. This present study is designed to investigate the metabolic profile of esculin in vivo based on ultra high performance liquid chromatography coupled to Fourier transform ion cyclotron resonance mass spectrometry (UHPLC-FT-ICR-MS) for the first time. After oral administration of esculin (100 mg/kg) for rats, plasma, urine, feces and bile samples were collected to screen metabolites. As a result, a total of 19 metabolites (10 phase I metabolites and 9 phase II metabolites) were found and identified. Results showed that metabolic pathways of esculin included hydrolysis, dehydrogenation, hydroxylation, methylation, dehydrogenation, glucuronidation, sulfation, and glycine conjugation. It was also found that after oral administration of esculin, the esculin could be metabolized to esculetin in vivo via deglycosylation, and esculetin was found in all biological samples. This study also laid solid basis for in-depth development of esculin and provided important information for clarifying the biotransformation process of esculin in vivo. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Identification of metabolites of vindoline in rats using ultra-high performance liquid chromatography/quadrupole time-of-flight mass spectrometry.

    PubMed

    Zhang, Yuqian; Sun, Yupeng; Mu, Xiyan; Yuan, Lin; Wang, Qiao; Zhang, Lantong

    2017-08-15

    Vindoline (VDL) is an indole alkaloid, possessing hypoglycemic and vasodilator effects, and it is also the prodrug of many vinca alkaloids. In this paper, we analyzed in vivo (including plasma, urine, bile and faeces) and in vitro metabolic profile of VDL in rat with ultra-high performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UHPLC-Q-TOF-MS/MS). The chromatographic separation was performed on a C 18 column with a mobile phase consisted of 3mM ammonium acetate buffer and acetonitrile at a flow rate of 300μL/min. The mass spectral analysis was conducted in a positive electrospray ionization mode, and on-line data acquisition method multiple mass defect filter (MMDF) combined with dynamic background subtraction (DBS) were used in the biological samples analysis to trace all the potential metabolites of VDL. Twenty-five metabolites of VDL were detected by comparing with the blank sample, of which there were 2 sulfate conjugates. These data suggested that the biotransformation of VDL was deacetylation, oxidation, deoxidization, methylation, dealkylation and sulfate conjugation. This study provides useful information for further study of the pharmacology and mechanism of VDL, meanwhile, the research method can be widely applied to speculate structural features of the metabolites of other vinca alkaloids. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Multianalyte, high-throughput liquid chromatography tandem mass spectrometry method for the sensitive determination of fungicides and insecticides in wine.

    PubMed

    Castro, Gabriela; Pérez-Mayán, Leticia; Rodríguez-Cabo, Tamara; Rodríguez, Isaac; Ramil, Maria; Cela, Rafael

    2018-01-01

    Evidence of pesticide transfer from grapes to wine, added to differences in the national regulations regarding the number and the maximum concentration of these species in wine, demands analytical procedures suitable for their routine control in this foodstuff. In this research, solid-phase extraction (SPE) and ultra-performance liquid chromatography (UPLC), with tandem mass spectrometry (MS/MS) detection, are combined to obtain a sensitive and rapid procedure to determine 50 pesticides in red and white wines. Efficiency and selectivity of sample preparation are correlated with the type of sorbent, the elution solvent, and the physicochemical properties of pesticides. SPE of 2-mL wine samples followed by direct injection of the extract in the UPLC-MS/MS system provides quantification limits (LOQs) below 1 ng mL -1 for 48 out of 50 compounds, linear responses up to 200 ng mL -1 , and acceptable accuracy, employing quantification against solvent-based standards, for 45 species. A total analysis time of 10 min, including compounds separation and re-equilibration of the UPLC column, was achieved. The developed methodology was applied to 25 wines (20 conventional and 5 ecological), produced in 7 different countries. Out of 27 pesticides quantified in these wines, 12 displayed occurrence frequencies above 24%; moreover, all wines, except one of the ecological ones, contained residues from at least one pesticide.

  14. Fast analysis of triterpenoids in Ganoderma lucidum spores by ultra-performance liquid chromatography coupled with triple quadrupole mass spectrometry.

    PubMed

    Yan, Zhou; Xia, Bing; Qiu, Ming Hua; Li Sheng, Ding; Xu, Hong Xi

    2013-11-01

    A rapid and reliable method was established for simultaneous determination of main triterpenoids in Ganoderma lucidum spores using ultra-high-performance liquid chromatography coupled with triple quadrupole mass spectrometry (UPLC-TQ-MS). The established method was validated in terms of linearity, sensitivity, precision, accuracy and stability, and was successfully applied to determine the contents of 10 main triterpenoids in different batches of G. lucidum spores. The analysis results showed that moderate levels of triterpenoids were found in G. lucidum spores. In addition, a MS full scan with a daughter ion scan experiment was performed to identify the potential derivatives of triterpenoids present in G. lucidum spores. As a result, a total of 22 triterpenoids from different G. lucidum spores were unequivocally or tentatively identified via comparisons with authentic standards and literatures. This method provides both qualitative and quantitative results without the need for repetitive UPLC-MS analyses, thereby increasing efficiency and productivity, making it suitable for high-throughput applications. Copyright © 2013 John Wiley & Sons, Ltd.

  15. Determination of Grayanotoxins from Rhododendron brachycarpum in Dietary Supplements and Homemade Wine by Liquid Chromatography-Quadrupole Time-of-Flight-Mass Spectrometry and Liquid Chromatography-Tandem Mass Spectrometry.

    PubMed

    Hwang, Taeik; Noh, Eunyoung; Jeong, Ji Hye; Park, Sung-Kwan; Shin, Dongwoo; Kang, Hoil

    2018-02-28

    A sensitive and specific high-performance liquid chromatography-quadrupole time-of-flight-mass spectrometry (LC-QTOF-MS) method combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed for the determination of grayanotoxins I and III in dietary supplements and homemade wine. Grayanotoxins I and III were successfully extracted using solid-phase extraction cartridges, characterized by LC-QTOF-MS, and quantitated by LC-MS/MS. The LC-MS/MS calibration curves were linear over concentrations of 10-100 ng/mL (grayanotoxin I) and 20-400 ng/mL (grayanotoxin III). Grayanotoxins I and III were found in 51 foodstuffs, with quantitative determinations revealing total toxin concentrations of 18.4-101 000 ng/mL (grayanotoxin I) and 15.3-56 000 ng/mL (grayanotoxin III). The potential of the validated method was demonstrated by successful quantitative analysis of grayanotoxins I and III in dietary supplements and homemade wine; the method appears suitable for the routine detection of grayanotoxins I and III from Rhododendron brachycarpum.

  16. Rapid and sensitive determination of benzo[a]pyrene in black ginseng using fluorescence detector and high performance liquid chromatography-tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    Cho, Hyun-jeong; Kim, Hye-jin; Son, Byeong-cheol; Jo, Dong-keun; Cho, Byung-lim

    2013-05-01

    Black ginseng is produced by steaming a ginseng root followed by drying repeatedly 9 times during the process and it is changed to be black color, so it is known that a black ginseng has more contents of saponins than red ginseng. However a fake black ginseng which is produced to be black color at high temperature in a short period of time generate carcinogenic benzo[a]pyrene(BaP) through the process. In this year, maximum residue level(MRL) for BaP was established to 2 ug/kg in black ginseng and more sensitive method was developed to quantitatively analyze the BaP by high performance liquid chromatography (HPLC) coupling with florescence detector and tandem mass spectrometry (atmospheric pressure chemical ionization-MS/MS). Chromatographic separation was performed on a Supelcosil™ LC-PAH column (3 μm, 3 mm x 50 mm). Mobile phase A was water and mobile phase B was acetonitrile. BaP was exactly separated from other 15 polycyclic aromatic hydrocarbons (PAHs) which have been selected as priority pollutants by the US Environmental Protection Agency (EPA). Linearity of detection was in the range of 0.2~20 μg/kg and limit of detection (LOD) for BaP was lower than 0.1 μg/kg, limit of quantification (LOQ) was 0.2 μg/kg. The recovery of Bap was 92.54%+/-6.3% in black ginseng.

  17. Metabolites profile of Gualou Xiebai Baijiu decoction (a classical traditional Chinese medicine prescription) in rats by ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    Lin, Pei; Qin, Zifei; Yao, Zhihong; Wang, Li; Zhang, Weiyang; Yu, Yang; Dai, Yi; Zhou, Hua; Yao, Xinsheng

    2018-05-15

    Gualou Xiebai Baijiu decoction (GLXB), a well-known classic traditional Chinese medicine prescription, has been widely used to treat coronary heart diseases for thousands of years in Eastern Asian countries due to its remarkable clinical effect. However, due to lack of in vivo metabolism research, the chemical components responsible for the therapeutic effects still remain unclear. In this work, a reliable "representative structure based homologous xenobiotics identification" (RSBHXI) strategy based on ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (UPLC/Q-TOF-MS) were applied to investigate the chemical components in GLXB extracts. As a result, 133 chemical components were characterized based on summarized fragmentation patterns, of which 41 components were confirmed unambiguously with authentic standards. Furthermore, a total of 138 GLXB-related xenobiotics were identified or tentatively characterized after oral administration of GLXB extracts. Moreover, to better understand the metabolic pathways of characteristic components in GLXB, metabolites profiles of five steroidal saponins and two flavonoids were performed, respectively. Since the metabolic pathways of five representative saponins had been finished in our previous study, we focused on the in vivo metabolism of two flavonoids. A total of 36 and 20 metabolites were detected in rat biological samples after oral administration of luteolin-7-O-β-D-glucopyranoside and rutin, respectively. The results indicated that dehydration, hydrolysis, hydroxylation, methylation, glucuronidation and sulfation were the main metabolic reactions, following the metabolic soft spots of GLXB-related flavonoids. Taken altogether, this study would be helpful for the further pharmacokinetics, pharmacological evaluation and quality control of GLXB. Copyright © 2018. Published by Elsevier B.V.

  18. Derivatization reagents in liquid chromatography/electrospray ionization tandem mass spectrometry.

    PubMed

    Santa, Tomofumi

    2011-01-01

    Liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) is one of the most prominent analytical techniques owing to its inherent selectivity and sensitivity. In LC/ESI-MS/MS, chemical derivatization is often used to enhance the detection sensitivity. Derivatization improves the chromatographic separation, and enhances the mass spectrometric ionization efficiency and MS/MS detectability. In this review, an overview of the derivatization reagents which have been applied to LC/ESI-MS/MS is presented, focusing on the applications to low molecular weight compounds. 2010 John Wiley & Sons, Ltd.

  19. Rapid quantification of pharmaceuticals and pesticides in passive samplers using ultra high performance liquid chromatography coupled to high resolution mass spectrometry.

    PubMed

    Wille, Klaas; Claessens, Michiel; Rappé, Karen; Monteyne, Els; Janssen, Colin R; De Brabander, Hubert F; Vanhaecke, Lynn

    2011-12-23

    The presence of both pharmaceuticals and pesticides in the aquatic environment has become a well-known environmental issue during the last decade. An increasing demand however still exists for sensitive and reliable monitoring tools for these rather polar contaminants in the marine environment. In recent years, the great potential of passive samplers or equilibrium based sampling techniques for evaluation of the fate of these contaminants has been shown in literature. Therefore, we developed a new analytical method for the quantification of a high number of pharmaceuticals and pesticides in passive sampling devices. The analytical procedure consisted of extraction using 1:1 methanol/acetonitrile followed by detection with ultra-high performance liquid chromatography coupled to high resolution and high mass accuracy Orbitrap mass spectrometry. Validation of the analytical method resulted in limits of quantification and recoveries ranging between 0.2 and 20 ng per sampler sheet and between 87.9 and 105.2%, respectively. Determination of the sampler-water partition coefficients of all compounds demonstrated that several pharmaceuticals and most pesticides exert a high affinity for the polydimethylsiloxane passive samplers. Finally, the developed analytical methods were used to measure the time-weighted average (TWA) concentrations of the targeted pollutants in passive samplers, deployed at eight stations in the Belgian coastal zone. Propranolol, carbamazepine and seven pesticides were found to be very abundant in the passive samplers. These obtained long-term and large-scale TWA concentrations will contribute in assessing the environmental and human health risk of these emerging pollutants. Copyright © 2011 Elsevier B.V. All rights reserved.

  20. Profiling pneumococcal type 3-derived oligosaccharides by high resolution liquid chromatography-tandem mass spectrometry

    PubMed Central

    Li, Guoyun; Li, Lingyun; Xue, Changhu; Middleton, Dustin; Linhardt, Robert J.; Avci, Fikri Y.

    2015-01-01

    Pneumococcal type-3 polysaccharide (Pn3P) is considered a major target for the development of a human vaccine to protect against Streptococcus pneumonia infection. Thus, it is critical to develop methods for the preparation and analysis of Pn3P-derived oligosaccharides to better understand its immunological properties. In this paper, we profile oligosaccharides, generated by the free radical depolymerization of Pn3P, using liquid chromatography (LC)-tandem mass spectrometry (MS/MS). Hydrophilic liquid interaction chromatography (HILIC)-mass spectrometry (MS) revealed a series of oligosaccharides with an even- and odd-number of saccharide residues, ranging from monosaccharide, degree of polymerization (dp1) to large oligosaccharides up to dp 20, generated by free radical depolymerization. Isomers of oligosaccharides with an even number of sugar residues were easily separated on a HILIC column, and their sequences could be distinguished by comparing MS/MS of these oligosaccharides and their reduced alditols. Fluorescent labeling with 2-aminoacridone (AMAC) followed by reversed phase (RP)-LC-MS/MS was applied to analyze and sequence poorly separated product mixtures, as RP-LC affords higher resolution of AMAC-labeled oligosaccharides than does HILIC-based separation. The present methodology can be potentially applied to profiling other capsular polysaccharides. PMID:25913329

  1. Profiling pneumococcal type 3-derived oligosaccharides by high resolution liquid chromatography-tandem mass spectrometry.

    PubMed

    Li, Guoyun; Li, Lingyun; Xue, Changhu; Middleton, Dustin; Linhardt, Robert J; Avci, Fikri Y

    2015-06-05

    Pneumococcal type-3 polysaccharide (Pn3P) is considered a major target for the development of a human vaccine to protect against Streptococcus pneumoniae infection. Thus, it is critical to develop methods for the preparation and analysis of Pn3P-derived oligosaccharides to better understand its immunological properties. In this paper, we profile oligosaccharides, generated by the free radical depolymerization of Pn3P, using liquid chromatography (LC)-tandem mass spectrometry (MS/MS). Hydrophilic liquid interaction chromatography (HILIC)-mass spectrometry (MS) revealed a series of oligosaccharides with an even- and odd-number of saccharide residues, ranging from monosaccharide, degree of polymerization (dp1) to large oligosaccharides up to dp 20, generated by free radical depolymerization. Isomers of oligosaccharides with an even number of sugar residues were easily separated on a HILIC column, and their sequences could be distinguished by comparing MS/MS of these oligosaccharides and their reduced alditols. Fluorescent labeling with 2-aminoacridone (AMAC) followed by reversed phase (RP)-LC-MS/MS was applied to analyze and sequence poorly separated product mixtures, as RP-LC affords higher resolution of AMAC-labeled oligosaccharides than does HILIC-based separation. The present methodology can be potentially applied to profiling other capsular polysaccharides. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. [Determination of deoxynivalenol in grain and its products by solid-phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Huang, Juan; Chen, Guosong; Zhang, Xiaoyan; Shen, Chongyu; Lü, Chen; Wu, Bin; Liu, Yan; Chen, Huilan; Ding, Tao

    2012-11-01

    A method was established for the determination of deoxynivalenol (vomitoxin) in grain and its products based on solid-phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The sample was firstly extracted by acetonitrile-water (84:16, v/v). The extract was then cleaned-up by an HLB solid phase extraction cartridge. The separation was carried out on a Phenomenex Kinetex C18 column (100 mm x4. 6 mm, 2.6 microm) with a gradient elution using 0.3% per hundred ammonia solution-acetonitrile as mobile phases. The analysis of deoxynivalenol was performed under electrospray negative ionization mode. The limit of detection (LOD, S/N= 3) and the limit of quantification (LOQ, S/N = 10) were 20 microg/kg and 50 microg/kg, respectively. A good linearity (r > 0.99) was achieved for the target compound over the range of 20-1000 pg/L. The recoveries at the three spiked levels (50, 100, 500 microg/kg) in the blank matrices such as flour, barley, soybean, rice, cornmeal, cassava and wheat, were varied from 75.6% to 111.0% with the relative standard deviations no more than 13. 0%. The method is accurate, efficient, sensitive and practical. The cost of pretreatment is obviously reduced by replacing immunoaffinity columns and Mycosep columns with HLB columns which have the same purification effect.

  3. Dried Blood Spots Combined With Ultra-High-Performance Liquid Chromatography-Mass Spectrometry for the Quantification of the Antipsychotics Risperidone, Aripiprazole, Pipamperone, and Their Major Metabolites.

    PubMed

    Tron, Camille; Kloosterboer, Sanne M; van der Nagel, Bart C H; Wijma, Rixt A; Dierckx, Bram; Dieleman, Gwen C; van Gelder, Teun; Koch, Birgit C P

    2017-08-01

    Risperidone, aripiprazole, and pipamperone are antipsychotic drugs frequently prescribed for the treatment of comorbid behavioral problems in children with autism spectrum disorders. Therapeutic drug monitoring (TDM) could be useful to decrease side effects and to improve patient outcome. Dried blood spot (DBS) sample collection seems to be an attractive technique to develop TDM of these drugs in a pediatric population. The aim of this work was to develop and validate a DBS assay suitable for TDM and home sampling. Risperidone, 9-OH risperidone, aripiprazole, dehydroaripiprazole, and pipamperone were extracted from DBS and analyzed by ultra-high-performance liquid chromatography-tandem mass spectrometry using a C18 reversed-phase column with a mobile phase consisting of ammonium acetate/formic acid in water or methanol. The suitability of DBS for TDM was assessed by studying the influence of specific parameters: extraction solution, EDTA carryover, hematocrit, punching location, spot volume, and hemolysis. The assay was validated with respect to conventional guidelines for bioanalytical methods. The method was linear, specific without any critical matrix effect, and with a mean recovery around 90%. Accuracy and imprecision were within the acceptance criteria in samples with hematocrit values from 30% to 45%. EDTA or hemolysis did not skew the results, and no punching carryover was observed. No significant influence of the spot volume or the punch location was observed. The antipsychotics were all stable in DBS stored 10 days at room temperature and 1 month at 4 or -80°C. The method was successfully applied to quantify the 3 antipsychotics and their metabolites in patient samples. A UHPLC-MS/MS method has been successfully validated for the simultaneous quantification of risperidone, 9-OH risperidone, aripiprazole, dehydroaripiprazole, and pipamperone in DBS. The assay provided good analytical performances for TDM and clinical research applications.

  4. Determination of six microcystins and nodularin in surface and drinking waters by on-line solid phase extraction-ultra high pressure liquid chromatography tandem mass spectrometry.

    PubMed

    Beltrán, Eduardo; Ibáñez, María; Sancho, Juan Vicente; Hernández, Félix

    2012-11-30

    Microcystins and nodularin are cyclic peptides hepatotoxins produced by cyanobacterial genera (blue-green algae). Toxic cyanobacterial blooms are a worldwide problem, as reported in several countries, like China, Australia, or the United States. Therefore, it is necessary to develop sensitive and reliable analytical methodology to determine this type of toxins in water at parts per billion levels, or even lower. In this work, the potential of solid-phase extraction coupled on-line to ultra-high-pressure liquid chromatography/electrospray tandem mass spectrometry (SPE-UHPLC-MS/MS) has been investigated for the efficient quantification and confirmation of microcystins LR, RR, YR, LY, LW, LF and nodularin in surface and drinking water samples, at sub-ppb levels. The method developed involves the injection of only 1 mL of water sample into the on-line SPE-UHPLC-MS/MS system and allows the rapid determination of the compounds selected (8 min of chromatographic run), avoiding laborious sample treatment. The method was validated in surface and drinking water by means of recovery experiments at 0.25 and 1 μg L(-1). Average recoveries (n=5) ranged from 71 to 116%, with relative standard deviations (RSDs) lower than 15%. For microcystins LR, RR, YR and nodularin, a third level was also assayed (0.1 μg L(-1)) obtaining satisfactory data too. Limits of detection between 0.002 and 0.0405 μg L(-1) were estimated (0.0005 μg L(-1) for nodularin). The developed method was applied to the analysis of water samples collected in the province of Castellón (Spain). The acquisition of three MS/MS transitions for each compound allowed the unequivocal confirmation of positive samples, which was supported by the accomplishment of ion intensity ratios and retention time when compared with reference standards. Copyright © 2012 Elsevier B.V. All rights reserved.

  5. Semiautomated determination of neonicotinoids and characteristic metabolite in urine samples using TurboFlow™ coupled to ultra high performance liquid chromatography coupled to Orbitrap analyzer.

    PubMed

    López-García, Marina; Romero-González, Roberto; Lacasaña, Marina; Garrido Frenich, Antonia

    2017-11-30

    A semiautomated method based on ultra-high performance liquid chromatography (UHPLC) coupled to Orbitrap high resolution mass spectrometry has been developed for the determination of neonicotinoids (imidacloprid, acetamiprid, clothianidin, dinotefuran, nitenpyram, thiacloprid and thiamethoxam) and the metabolite acetamiprid-n-desmethyl in urine samples. Two automated methods were tested (solid-phase extraction "SPE" and turbulent flow chromatography "TurboFlow™"), obtaining the best results when TurboFlow™ was applied. The total analysis time for the developed method was 14min. The optimized method was validated, obtaining suitable results for all validation parameters. Recoveries ranged from 78% to 116% meanwhile repeatability and reproducibility were evaluated obtaining values lower than 10% and 20% respectively (except for dinotefuran and nitenpyram at 0.2μgL -1 ). The limit of quantification (LOQ) for all compounds was established at 0.2μgL -1 . The proposed analytical methodology was applied to analyze the target compounds in thirty six urine samples from pregnant women living in agricultural areas of Almería (Spain). Imidacloprid, acetamiprid and acetamiprid-n-desmethyl were detected in some of the samples at concentrations ranging from 0.23 to 1.57μgL -1 . Furthermore, dinotefuran was identified in two samples at trace levels. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Ultra performance liquid chromatography atmospheric pressure photoionization high resolution mass spectrometric method for determination of multiclass pesticide residues in grape and mango juices.

    PubMed

    Deme, Pragney; Upadhyayula, Vijayasarathi V R

    2015-04-15

    A novel analytical method was developed for determination of organochlorine, synthetic pyrethroid, organophosphate and carbamate pesticide residues in fruit juices using ultra performance liquid chromatography-atmospheric pressure photoionization-high resolution mass spectrometry (UPLC-APPI-HRMS). The analytes were extracted from fruit juices by dispersive solid-phase extraction using multi-walled carbon nanotubes (MWCNTs). The analysis was carried out in full scan mode using dual ionization mode of APPI in the mass range of 100-650 units. The limit of detection and limit of quantification values for the pesticides were in the range of 0.025-0.15 ng mL(-1) and 0.1-0.5 ng mL(-1) respectively. The matrix effect of the method was found to be low and extraction recoveries were in the range of 60-110%. Some of the real fruits juice samples showed the presence of some pesticides in the range of 6.5-24.8 ng L(-1). Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. [Determination of morroniside concentration in beagle plasma and its pharmacokinetics by high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Xiong, Shan; Li, Jinglai; Zhu, Xiuqing; Wang, Xiaoying; Lü, Guiyuan; Zhang, Zhenqing

    2014-03-01

    A sensitive, simple and specific high performance liquid chromatography-electrospray ionization tandem mass spectrometry (LC-MS/MS) method was developed for the determination of morroniside in the plasma of beagles administered via intragastric (ig) doses of morroniside. The method employed paeoniflorin as the internal standard and extracted by simple protein precipitation. The separation was achieved using an Inertsil ODS-SP column (50 mm x 2.1 mm, 5 microm) with mobile phases of 1 mmol/L sodium formate aqueous solution and acetonitrile (gradient elution) at a flow rate of 0.4 mL/min. The detection was accomplished by a mass spectrometer using multiple reaction monitoring (MRM) in positive mode. Pharmacokinetic parameters were fitted by software DAS 2.0. The methodological study showed a good linear relationship of 2-5 000 microg/L (r = 0.996 6) with a sensitivity of 2 microg/L as the limit of quantification. The precision, accuracy, mean recoveries and the matrix effects were satisfied with the requirements of biological sample measurement. The method described above was successfully applied to the pharmacokinetic study of morroniside in the beagle plasma samples. The area under the plasma concentration-time curves (AUC(0-infinity)) of morroniside after single ig administration doses of 5, 15 and 45 mg/kg were (1 631.20 +/- 238.50), (3 984.05 +/- 750.38) and (10 397.64 +/- 3 156.34) microg/L x h. The relationship between dose and AUC showed a good linearity. The pharmacokinetic property of morroniside was proposed to be linear pharmacokinetics.

  8. Simultaneous determination of kasugamycin and validamycin-A residues in cereals by consecutive solid-phase extraction combined with liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhang, Hong; Wang, Chenchen; Li, Huidong; Nie, Yan; Fang, Liping; Chen, Zilei

    2018-03-01

    Two polar aminoglycosides, kasugamycin and validamycin-A, were determined in cereals (brown rice, wheat and corn) by high-performance liquid chromatography-tandem mass spectrometry. The analytes were extracted from samples using methanol and water (70:30, v/v) at pH 5.5, purified using both a hydrophilic-hydrophobic-balanced cartridge and a strong cation-exchange cartridge, and then analysed using multiple reaction monitoring in positive electrospray ionisation mode with a special ReproSil 100 C 18 high-performance liquid chromatography column. This newly proposed method yielded good sensitivity and excellent chromatographic performance. The limits of quantification for kasugamycin and validamycin-A were 4.1 µg/kg and 1.0 µg/kg, respectively. The recoveries for both compounds at three fortification levels (4, 100 and 500 µg/kg for kasugamycin; 1, 10 and 100 µg/kg for validamycin-A) ranged from 75% to 110%, and the relative standard deviations were below 15%.

  9. Ultra-high performance supercritical fluid chromatography of lignin-derived phenols from alkaline cupric oxide oxidation.

    PubMed

    Sun, Mingzhe; Lidén, Gunnar; Sandahl, Margareta; Turner, Charlotta

    2016-08-01

    Traditional chromatographic methods for the analysis of lignin-derived phenolic compounds in environmental samples are generally time consuming. In this work, an ultra-high performance supercritical fluid chromatography method with a diode array detector for the analysis of major lignin-derived phenolic compounds produced by alkaline cupric oxide oxidation was developed. In an analysis of a collection of 11 representative monomeric lignin phenolic compounds, all compounds were clearly separated within 6 min with excellent peak shapes, with a limit of detection of 0.5-2.5 μM, a limit of quantification of 2.5-5.0 μM, and a dynamic range of 5.0-2.0 mM (R(2) > 0.997). The new ultra-high performance supercritical fluid chromatography method was also applied for the qualitative and quantitative analysis of lignin-derived phenolic compounds obtained upon alkaline cupric oxide oxidation of a commercial humic acid. Ten out of the previous eleven model compounds could be quantified in the oxidized humic acid sample. The high separation power and short analysis time obtained demonstrate for the first time that supercritical fluid chromatography is a fast and reliable technique for the analysis of lignin-derived phenols in complex environmental samples. © 2016 The Authors, Journal of Separation Science Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Separation of enantiomers of new psychoactive substances by high-performance liquid chromatography.

    PubMed

    Kadkhodaei, Kian; Forcher, Lisa; Schmid, Martin G

    2018-03-01

    New psychoactive substances are defined as compounds with consciousness-changing effects and have been developed simultaneously with classical drugs. They arise through structural modifications of illegal substances and are mainly produced to circumvent laws. Availability is simple, since new psychoactive substances can be purchased from the Internet. Among them many chemical drug compound classes are chiral and thus the two resulting enantiomers can differ in their effects. The aim of this study is to develop a suitable chiral high-performance liquid chromatography separation method for a broad spectrum of new psychoactive substances using cellulose tris(3,5-dichlorophenylcarbamate) as a chiral selector. Experiments were performed by high-performance liquid chromatography in normal-phase mode under isocratic conditions using ultraviolet detection. Direct separation was carried out on a high-performance liquid chromatography column (Lux® i-Cellulose-5, 3.5 μm, Phenomenex®), available since 2016. Excellent separation results were obtained for cathinones. After further optimization, even 47 instead of 39 out of 52 cathinones showed baseline separation. For amphetamine derivatives, satisfactory results were not achieved. Further, new psychoactive substances from other compound classes such as benzofuranes, thiophenes, phenidines, phenidates, morpholines, and ketamines were partially resolved, depending on the polarity and degree of substitution. All analytes, which were mainly purchased from the Internet, were proven to be traded as racemates. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Coupling ultra high-pressure liquid chromatography with mass spectrometry: constraints and possible applications.

    PubMed

    Rodriguez-Aller, Marta; Gurny, Robert; Veuthey, Jean-Luc; Guillarme, Davy

    2013-05-31

    The introduction of columns packed with porous sub-2μm particles and the extension of the upper pressure limit of HPLC instrumentation to 1300bar (ultra-high pressure liquid chromatography, UHPLC) has opened new frontiers in resolution and speed of analysis. However, certain constraints appear when coupling UHPLC technology with mass spectrometry (MS). First, the most significant limitation is related to the narrow peaks that are produced by UHPLC that require a fast duty cycle, which is only available on the latest generations of MS devices. Thus, certain analyzers are more readily compatible with UHPLC (e.g., QqQ or TOF/MS) than others (e.g., ion trap or FT-MS). Second, due to the reduction of the column volume, extra-column band broadening can become significant, leading to a reduction in the kinetic performance of the UHPLC-MS configuration. Third, as the mobile phase linear velocity is higher in UHPLC, the electrospray ionization source must also be able to provide high sensitivity at flow rates of up to 1mL/min. Despite these limitations, the UHPLC-MS/MS platform has successfully been employed over the last decade for various types of applications, including those related to bioanalysis, drug metabolism, multi-residue screening, metabolomics, biopharmaceuticals and polar compounds. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. A highly selective dispersive liquid-liquid microextraction approach based on the unique fluorous affinity for the extraction and detection of per- and polyfluoroalkyl substances coupled with high performance liquid chromatography tandem-mass spectrometry.

    PubMed

    Wang, Juan; Shi, Yali; Cai, Yaqi

    2018-04-06

    In the present study, a highly selective fluorous affinity-based dispersive liquid-liquid microextraction (DLLME) technique was developed for the extraction and analysis of per- and polyfluoroalkyl substances (PFASs) followed by high performance liquid chromatography tandem-mass spectrometry. Perfluoro-tert-butanol with multiple C-F bonds was chosen as the extraction solvent, which was injected into the aqueous samples with a dispersive solvent (acetonitrile) in a 120:800 (μL, v/v) mixture for PFASs enrichment. The fluorous affinity-based extraction mechanism was confirmed by the significantly higher extraction recoveries for PFASs containing multiple fluorine atoms than those for compounds with fewer or no fluorine atoms. The extraction recoveries of medium and long-chain PFASs (CF 2  > 5) exceeded 70%, except perfluoroheptanoic acid, while those of short-chain PFASs were lower than 50%, implying that the proposed DLLME may not be suitable for their extraction due to weak fluorous affinity. This highly fluoroselective DLLME technique can greatly decrease the matrix effect that occurs in mass spectrometry detection when applied to the analysis of urine samples. Under the optimum conditions, the relative recoveries of PFASs with CF 2  > 5 ranged from 80.6-121.4% for tap water, river water and urine samples spiked with concentrations of 10, 50 and 100 ng/L. The method limits of quantification for PFASs in water and urine samples were in the range of 0.6-8.7 ng/L. Furthermore, comparable concentrations of PFASs were obtained via DLLME and solid-phase extraction, confirming that the developed DLLME technique is a promising method for the extraction of PFASs in real samples. Copyright © 2018 Elsevier B.V. All rights reserved.

  13. Polydopamine-coated magnetic nanoparticles for isolation and enrichment of estrogenic compounds from surface water samples followed by liquid chromatography-tandem mass spectrometry determination.

    PubMed

    Capriotti, Anna Laura; Cavaliere, Chiara; La Barbera, Giorgia; Piovesana, Susy; Samperi, Roberto; Zenezini Chiozzi, Riccardo; Laganà, Aldo

    2016-06-01

    Estrogens, phytoestrogens, and mycoestrogens may enter into the surface waters from different sources, such as effluents of municipal wastewater treatment plants, industrial plants, and animal farms and runoff from agricultural areas. In this work, a multiresidue analytical method for the determination of 17 natural estrogenic compounds, including four steroid estrogens, six mycoestrogens, and seven phytoestrogens, in river water samples has been developed. (Fe3O4)-based magnetic nanoparticles coated by polydopamine (Fe3O4@pDA) were used for dispersive solid-phase extraction, and the final extract was analyzed by ultra-high performance liquid chromatography coupled with tandem mass spectrometry. The Fe3O4 magnetic nanoparticles were prepared by a co-precipitation procedure, coated by pDA, and characterized by scanning electron microscopy, infrared spectroscopy, and elemental analysis. The sample preparation method was optimized in terms of extraction recovery, matrix effect, selectivity, trueness, precision, method limits of detection, and method limits of quantification (MLOQs). For all the 17 analytes, recoveries were >70 % and matrix effects were below 30 % when 25 mL of river water sample was treated with 90 mg of Fe3O4@pDA nanoparticles. Selectivity was tested by spiking river water samples with 50 other compounds (mycotoxins, antibacterials, conjugated hormones, UV filters, alkylphenols, etc.), and only aflatoxins and some benzophenones showed recoveries >60 %. This method proved to be simple and robust and allowed the determination of natural estrogenic compounds belonging to different classes in surface waters with MLOQs ranging between 0.003 and 0.1 μg L(-1). Graphical Abstract Determination of natural estrogenic compounds in water by magnetic solid phase extraction followed by liquid chromatography-tandem mass spectrometry analysis.

  14. Determination of chloroacetanilide herbicide metabolites in water using high-performance liquid chromatography-diode array detection and high-performance liquid chromatography/mass spectrometry

    USGS Publications Warehouse

    Hostetler, K.A.; Thurman, E.M.

    2000-01-01

    Analytical methods using high-performance liquid chromatography-diode array detection (HPLC-DAD) and high-performance liquid chromatography/mass spectrometry (HPLC/MS) were developed for the analysis of the following chloroacetanilide herbicide metabolites in water: alachlor ethanesulfonic acid (ESA); alachlor oxanilic acid; acetochlor ESA; acetochlor oxanilic acid; metolachlor ESA; and metolachlor oxanilic acid. Good precision and accuracy were demonstrated for both the HPLC-DAD and HPLC/MS methods in reagent water, surface water, and ground water. The average HPLC-DAD recoveries of the chloroacetanilide herbicide metabolites from water samples spiked at 0.25, 0.5 and 2.0 ??g/l ranged from 84 to 112%, with relative standard deviations of 18% or less. The average HPLC/MS recoveries of the metabolites from water samples spiked at 0.05, 0.2 and 2.0 ??g/l ranged from 81 to 118%, with relative standard deviations of 20% or less. The limit of quantitation (LOQ) for all metabolites using the HPLC-DAD method was 0.20 ??g/l, whereas the LOQ using the HPLC/MS method was at 0.05 ??g/l. These metabolite-determination methods are valuable for acquiring information about water quality and the fate and transport of the parent chloroacetanilide herbicides in water. Copyright (C) 2000 Elsevier Science B.V.

  15. Chemical profiling of Qixue Shuangbu Tincture by ultra-performance liquid chromatography with electrospray ionization quadrupole-time-of-flight high-definition mass spectrometry (UPLC-QTOF/MS).

    PubMed

    Chen, Lin-Wei; Wang, Qin; Qin, Kun-Ming; Wang, Xiao-Li; Wang, Bin; Chen, Dan-Ni; Cai, Bao-Chang; Cai, Ting

    2016-02-01

    The present study was designed to develop and validate a sensitive and reliable ultra high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-QTOF/MS) method to separate and identify the chemical constituents of Qixue Shuangbu Tincture (QXSBT), a classic traditional Chinese medicine (TCM) prescription. Under the optimized UPLC and QTOF/MS conditions, 56 components in QXSBT, including chalcones, triterpenoids, protopanaxatriol, flavones and flavanones were identified and tentatively characterized within a running time of 42 min. The components were identified by comparing the retention times, accurate mass, and mass spectrometric fragmentation characteristic ions, and matching empirical molecular formula with that of the published compounds. In conclusion, the established UPLC-QTOF/MS method was reliable for a rapid identification of complicated components in the TCM prescriptions. Copyright © 2016 China Pharmaceutical University. Published by Elsevier B.V. All rights reserved.

  16. Ultra-performance liquid chromatography fingerprinting for quality control of Phragmitis rhizoma (Lugen) produced in Baiyangdian

    PubMed Central

    Li, Hong; Gao, Yu-Mei; Zhang, Jing; Wang, Lin; Wang, Xiao-Xin

    2013-01-01

    Objective: To establish an ultra-performance liquid chromatography (UPLC) fingerprinting method for quality control of Phragmitis rhizoma from Baiyangdian. Materials and Methods: Ultrasonic extraction with 70% methanol was performed on 10 samples of P. rhizoma collected from 10 different villages in Baiyangdian. The sample solutions were analyzed by Waters UPLC equipped with the ACQUITY UPLC BEH C18 column and photodiode array (PDA) detector, and gradient eluted with acetonitrile/water as the mobile phase. The flow rate was set to 0.1 mL/min; the column temperature was set to 25°C; and the detection wavelength was set to 285 nm. Results: The chromatograms of the 10 samples showed 27 common peaks, of which one was identified as the ferulic acid standard. The similarity indexes were all above 0.82. Hierarchical cluster analysis showed that the constituents and their quantities differed according to the diameter of the original plant, which is related to its age. Conclusion: The UPLC fingerprinting method had the advantages of being fast, accurate, and highly efficient; this indicated that it can be used for quality control of P. rhizoma produced in Baiyangdian. Also, the relation between the quality and diameter/age of the plant needs to be further investigated. PMID:24124278

  17. Ultra high performance liquid chromatography coupled with electrospray ionization/quadrupole time-of-flight mass spectrometry for the rapid analysis of constituents in the traditional Chinese medicine formula Wu Ji Bai Feng Pill.

    PubMed

    Duan, Shengnan; Qi, Wen; Zhang, Siwen; Huang, Kunkun; Yuan, Dan

    2017-10-01

    An ultra high performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight mass spectrometry method in both positive and negative ion modes was established in order to comprehensively investigate the major constituents in Wu Ji Bai Feng Pill. Briefly, a Waters ACQUITY UPLC HSS C 18 column was used to separate the aqueous extract of Wu Ji Bai Feng Pill. A total of 0.1% formic acid in acetonitrile and 0.1% aqueous formic acid v/v were used as the mobile phase. All analytes were determined using quadrupole time-of-flight mass spectrometry with electrospray ionization source in positive and negative ion modes. At length, a total of 173 components including flavones and their glycosides, monoterpene glycosides, triterpene saponins, phenethylalchohol glycosides, iridoid glycosides, phthalides, tanshinones, phenolic acids, sesquiterpenoids and cyclopeptides were identified or tentatively characterized in Wu Ji Bai Feng Pill in an analysis of 16.0 min based on the accurate mass and tandem mass spectrometry behaviors. The developed method is rapid and highly sensitive to characterize the chemical constituents of Wu Ji Bai Feng Pill, which could not only be used for chemical standardization and quality control of Wu Ji Bai Feng Pill, but also be helpful for further study in vivo metabolism of Wu Ji Bai Feng Pill. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Simultaneous determination of four water-soluble vitamins in fortified infant foods by ultra-performance liquid chromatography coupled with triple quadrupole mass spectrometry.

    PubMed

    Lu, Baiyi; Ren, Yiping; Huang, Baifen; Liao, Wenqun; Cai, Zengxuan; Tie, Xiaowei

    2008-03-01

    A novel ultra-performance liquid chromatography electrospray ionization tandem triple quadrupole mass spectrometry method for the simultaneous determination of four water-soluble vitamins, including vitamin B5 (VB5), vitamin B8 (VB8), vitamin B9 (VB9), and vitamin B12 (VB12) in fortified infant foods is developed and validated. A reverse phase UPLC separation system consisting of a Waters ACQUITY UPLC BEH C-18 column (2.1 mm x 100 mm i.d., 1.7 microm) and a binary gradient acetonitrile-water mobile phase is applied for the separation of the four water-soluble vitamins. Formic acid is spiked into the mobile phase to enhance the ionization efficiency. Tandem MS-MS analysis is performed in multi-reaction monitoring mode (MRM). Product-ion traces at m/z 220.1 --> 89.9 for VB5, 245.1 --> 227.1 for VB8, 442.3 --> 295.2 for VB9, and 678.9 --> 147.0 for VB12 are used for quantitation of the corresponding vitamins, and traces at m/z 455.5 --> 308.0 are used for methotrexate (internal standard). Limits of quantitation (LOQs) are 0.016, 0.090, 0.020, and 0.019 microg/L for VB5, VB8, VB9, and VB12, respectively. Intra- and inter-day precisions for the determination of the four vitamins are better than 6.84% and 12.26% in relative standard deviations, and recoveries for the four vitamins are in the range of 86.0~101.5%. The developed approach is applied for the determination of the trace amounts of the vitamins in fortified milk powers and fortified rice powers.

  19. Assessing the detectability of antioxidants in two-dimensional high-performance liquid chromatography.

    PubMed

    Bassanese, Danielle N; Conlan, Xavier A; Barnett, Neil W; Stevenson, Paul G

    2015-05-01

    This paper explores the analytical figures of merit of two-dimensional high-performance liquid chromatography for the separation of antioxidant standards. The cumulative two-dimensional high-performance liquid chromatography peak area was calculated for 11 antioxidants by two different methods--the areas reported by the control software and by fitting the data with a Gaussian model; these methods were evaluated for precision and sensitivity. Both methods demonstrated excellent precision in regards to retention time in the second dimension (%RSD below 1.16%) and cumulative second dimension peak area (%RSD below 3.73% from the instrument software and 5.87% for the Gaussian method). Combining areas reported by the high-performance liquid chromatographic control software displayed superior limits of detection, in the order of 1 × 10(-6) M, almost an order of magnitude lower than the Gaussian method for some analytes. The introduction of the countergradient eliminated the strong solvent mismatch between dimensions, leading to a much improved peak shape and better detection limits for quantification. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. 1-Adamantylamine a simple urine marker for screening for third generation adamantyl-type synthetic cannabinoids by ultra-performance liquid chromatography tandem mass spectrometry.

    PubMed

    Ford, Loretta T; Berg, Jonathan D

    2016-11-01

    Background Synthetic cannabinoids (NOIDS) are novel psychotropic drugs (NPS) currently freely sold in the United Kingdom as 'research chemicals'. Detection of NOIDS use is not available in current routine methods. Here we describe a marker which helps determine which patients have used these substances. Methods In a test case, ultra-performance liquid chromatography mass spectrometry (UPLC-Tof) was used to screen the legal high Herbal Haze II, the contents of hand-rolled cigarettes and five patient samples for NOIDS and their metabolites. Results Analysis of legal high Herbal Haze II and cigarettes identified the third generation adamantyl-type NOIDS N-(1-adamantyl)-1-pentyl-1H-indazole-3-carboxamide (AKB-48), 5F-AKB-48 and N-adamantyl-1-fluoropentylindole-3-carboxamide (STS-135). Out of 18 potential metabolites, 1-adamantylamine (C 10 H 17 N) was detected in all five urine samples. This adamantyl-type NOID marker was incorporated into our routine LC-MS/MS urine screen. Out of 14,436 random urine samples screened over eight months, 296 (2.05%) tested positive for the adamantyl-type NOID marker. Conclusion We have discovered a urine marker for identifying patients smoking legal high products containing the third generation adamantyl-type NOIDS such as AKB-48 and its fluoropentyl analogue 5F-AKB-48, which are among the most popular NOIDS currently available in legal high products sold in UK. This marker can be incorporated into routine LC-MS/MS drug screening alongside classic drugs of abuse. Positive detection rates for this new legal high marker are greater than for established classic drugs that are routinely screened such as amphetamine. This work highlights the need for a flexible toxicology screening service capable of adapting to changes in drug use such as the growing popularity of legal highs/NPS.

  1. Screening anti-tumor compounds from Ligusticum wallichii using cell membrane chromatography combined with high-performance liquid chromatography and mass spectrometry.

    PubMed

    Zhang, Tao; Ding, Yuanyuan; An, Hongli; Feng, Liuxin; Wang, Sicen

    2015-07-14

    Tyrosine 367 Cysteine-fibroblast growth factor receptor 4 cell membrane chromatography combined with high-performance liquid chromatography and mass spectrometry was developed. Tyrosine 367 Cysteine-HEK293 cells were used as cell membrane stationary phase. Specificity and reproducibility of the cell membrane chromatography was evaluated using 1-tert-butyl-3-{2-[4-(diethylamino)butylamino]-6-(3,5-dimethoxyphenyl)pyrido[2,3-d]pyrimidin-7-yl}urea, Nimodipine and dexamethasone acetate. Then, anti-tumor components acting on Tyrosine 367 Cysteine-fibroblast growth factor receptor 4 were screened and identified from extracts of Ligusticum wallichii. Components from the extract were retained on the cell membrane chromatographic column. The retained fraction was directly eluted into high-performance liquid chromatography with mass spectrometry system for separation and identification. Finally, Levistolide A was identified as an active component from Ligusticum wallichii extracts. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium bromide-formazan colorimetric assay revealed that Levistolide A inhibits proliferation of overexpressing the mutated receptor cells with dose-dependent manner. Phosphorylation of fibroblast growth factor receptor 4 was also decrease under Levistolide A treatment. Flex dock simulation verified that Levistolide A could bind with the tyrosine kinase domain of fibroblast growth factor receptor 4. Therefore, Levistolide A screened by the cell membrane chromatography combined with high-performance liquid chromatography and mass spectrometry can arrest cell growth. In conclusion, the two-dimensional high-performance liquid chromatography method can screen and identify potential anti-tumor ingredients which specifically act on the tyrosine kinase domain of the mutated fibroblast growth factor receptor 4. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  2. Regioisomeric and enantiomeric analyses of 24 designer cathinones and phenethylamines using ultra high performance liquid chromatography and capillary electrophoresis with added cyclodextrins.

    PubMed

    Li, Li; Lurie, Ira S

    2015-09-01

    DESIGNER: phenethylamines (PEAs) and cathinones have been encountered worldwide. Complete characterization of these substances can be challenging due to their chirality and variably substituted phenyl rings. In this study, 24 PEAs and cathinones were analyzed by ultra high performance liquid chromatography with photo diode array detection (UHPLC-PDA) on a variety of stationary phases, and by capillary electrophoresis on a dynamically coated capillary with PDA detection (CE-PDA). In the UHPLC-PDA study, a BEH Phenyl column resolved 18 of the 24 regioisomers in 8min, with good discrimination of the PEAs. In contrast, capillary zone electrophoresis (CZE) on a dynamically coated capillary partially or baseline resolved only 10 of the 24 regioisomers, but with improved discrimination of mono-substituted cathinones. A second series of CE-PDA experiments using 80mM (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD) in the run buffer resolved all 24 regioisomers and all but two sets of enantiomers within 18min. Five illicit samples were successfully analyzed using the described methods. Published by Elsevier Ireland Ltd.

  3. Characterisation of chemical components for identifying historical Chinese textile dyes by ultra high performance liquid chromatography - photodiode array - electrospray ionisation mass spectrometer.

    PubMed

    Han, Jing; Wanrooij, Jantien; van Bommel, Maarten; Quye, Anita

    2017-01-06

    This research makes the first attempt to apply Ultra High Performance Liquid Chromatography (UHPLC) coupled to both Photodiode Array detection (PDA) and Electrospray Ionisation Mass Spectrometer (ESI-MS) to the chemical characterisation of common textile dyes in ancient China. Three different extraction methods, respectively involving dimethyl sulfoxide (DMSO)-oxalic acid, DMSO and hydrochloric acid, are unprecedentedly applied together to achieve an in-depth understanding of the chemical composition of these dyes. The first LC-PDA-MS database of the chemical composition of common dyes in ancient China has been established. The phenomena of esterification and isomerisation of the dye constituents of gallnut, gardenia and saffron, and the dye composition of acorn cup dyed silk are clarified for the first time. 6-Hydroxyrubiadin and its glycosides are first reported on a dyed sample with Rubia cordifolia from China. UHPLC-PDA-ESI-MS with a C18 BEH shield column shows significant advantages in the separation and identification of similar dye constituents, particularly in the cases of analysing pagoda bud and turmeric dyed sample extracts. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Development of a high performance liquid chromatography method and a liquid chromatography-tandem mass spectrometry method with the pressurized liquid extraction for the quantification and confirmation of sulfonamides in the foods of animal origin.

    PubMed

    Yu, Huan; Tao, Yanfei; Chen, Dongmei; Wang, Yulian; Huang, Lingli; Peng, Dapeng; Dai, Menghong; Liu, Zhenli; Wang, Xu; Yuan, Zonghui

    2011-09-01

    The residues of sulfonamides (SAs) in the foods of animal origin are of the major concern because they are harmful to the consumer's health and could induce pathogens to develop resistance. Rapid and efficient determination methods are urgently in need. A quantitative high performance liquid chromatography method (HPLC) and a confirmative liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the simultaneous determination of 18 sulfonamides such as sulfamidinum, sulfanilamide, sulfisomidine, sulfadiazine, sulfapyridine, sulfathiazole, sulfamerazine, sulfadimidine, sulfamethoxypyridazine, sulfamethoxydiazine, sulfisoxazole, sulfachloropyridazine, sulfamethoxazole, sulfamonomethoxine, sulfadoxine, sulfaclozine, sulfadimethoxine, sulfaquinoxaline in the muscles, livers and kidneys of swine, bovine and chicken were developed and validated. The sample preparation procedures included a pressurized liquid extraction (PLE) with acetonitrile conducted at elevated temperature (70°C) and pressure (1400 psi). After clean-up with hydrophilic-lipophilic balance cartridge, the extraction solution was concentrated and analyzed by HPLC and LC-MS/MS analysis. 18 SAs were separated by the HPLC with a Zorbax SB-Aq-C18 column and the mobile phase of methanol/acetonitrile/1% acetic acid with a gradient system. The wavelength of UV for the HPLC detection was set at 285 nm. The LC-MS/MS analysis was achieved with a Hypersil Golden column and the mobile phase of acetonitrile and 0.1% formic acid aqueous solution with two gradient systems. The Limits of detection (LOD) and the limits of quantitation (LOQ) were 3 μg/kg and 10 μg/kg, respectively, for both of the HPLC and LC-MS/MS. Linearity was obtained with an average coefficient of determination (R) higher than 0.9980 over a dynamic range from the LOQ value up to 5000 μg/kg. The recoveries of the methods range from 71.1% to 118.3% with the relative standard derivation less than 13%. The peaks of interest with no interferences

  5. Quantification of sulfatides in dried blood and urine spots from metachromatic leukodystrophy patients by liquid chromatography/electrospray tandem mass spectrometry.

    PubMed

    Barcenas, Mariana; Suhr, Teryn R; Scott, C Ronald; Turecek, Frantisek; Gelb, Michael H

    2014-06-10

    Treatments are being developed for metachromatic leukodystrophy (MLD), suggesting the need for eventual newborn screening. Previous studies have shown that sulfatide molecular species are increased in the urine of MLD patients compared to samples from non-MLD individuals, but there is no data using dried blood spots (DBS), the most common sample available for newborn screening laboratories. We used ultra-high performance liquid chromatography/tandem mass spectrometry (UHPLC/MS/MS) to quantify sulfatides in DBS and dried urine spots from 14 MLD patients and 50 non-MLD individuals. Several sulfatide molecular species were increased in dried urine samples from all MLD samples compared to non-MLD samples. Sulfatides, especially low molecular species, were increased in DBS from MLD patients, but the sulfatide levels were relatively low. There was good separation in sulfatide levels between MLD and non-MLD samples when dried urine spots were used, but not with DBS, because DBS from non-MLD individuals have measurable levels of sulfatides. Sulfatide accumulation studies in urine, but not in DBS, emerges as the method of choice if newborn screening is to be proposed for MLD. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Analysis and Confirmation of 1,3-DMAA and 1,4-DMAA in Geranium Plants Using High Performance Liquid Chromatography with Tandem Mass Spectrometry at ng/g Concentrations

    PubMed Central

    Fleming, Heather L.; Ranaivo, Patricia L.; Simone, Paul S.

    2012-01-01

    1,3-Dimethylamylamine (1,3-DMAA) is a stimulant commercially sold in a variety of dietary supplements as a chemical species derived from geranium plants (Pelargonium graveolens). Whether 1,3-DMAA naturally occurs in geranium plants or other dietary ingredients, it has important regulatory and commercial ramifications. However, the analysis of 1,3-DMAA in geranium plants is not trivial due to low concentrations and a complex environmental matrix, requiring high selectivity and sensitivity. An extraction method combined with high performance liquid chromatography and tandem mass spectrometry is used to determine 1,3-DMAA and 1,4-dimethylamylamine (1,4-DMAA) concentrations in geranium plants with both external calibration and standard addition method. Samples from the Changzhou, Kunming, and Guiyang regions of China during both winter and summer were analyzed for 1,3-DMAA and 1,4-DMAA. The diastereomer ratios of the 1,3-DMAA stereoisomers of a racemic standard and the extracted plant were also quantified. PMID:23225994

  7. [Determination of capsaicinoids and eugenol in waste-edible-oil by liquid-liquid extraction and liquid chromatography-tandem mass spectrometry].

    PubMed

    Zhang, Zhong; Ren, Fei; Zhang, Pan

    2012-11-01

    A method was developed for the determination of capsaicinoids (capsaicin, dihydrocapsaicin and synthetic capsaicin) and eugenol in waste-edible-oil extracted by liquid-liquid extraction and liquid chromatography-tandem mass spectrometry (LC-MS/MS). The capsaicinoids and eugenol in waste-edible-oil were extracted by methanol, and then separated by a SUPEL COSIL ABZ + Plus dC18 column (150 mm x4.6 mm, 5 microm). The analysis was performed by MS/MS with electrospray ionization in positive and negative ion modes with multiple reaction monitoring (MRM). The limits of detection for capsaicin, dihydrocapsaicin, synthetic capsaicin and eugenol were 0.02, 0.03, 0.03 and 0.6 microg/L, respectively. The good linear relationships were obtained in certain concentration ranges of capsaicinoids and eugenol. The relative standard deviations (RSDs, n=5) of same-worker and different-worker were less than 5%. The method is exclusive, sensitive and accurate, and can be used in waste-edible-oil determination.

  8. Determination of tiropramide in human plasma by liquid chromatography-tandem mass spectrometry.

    PubMed

    Lee, Hye Won; Ji, Hye Young; Kim, Hee Hyun; Cho, Hea-Young; Lee, Yong-Bok; Lee, Hye Suk

    2003-11-05

    A rapid, sensitive and selective liquid chromatography-tandem mass spectrometric (LC/MS/MS) method for the determination of tiropramide in human plasma was developed. Tiropramide and internal standard, cisapride were extracted from human plasma by liquid-liquid extraction and analyzed on a Luna C8 column with the mobile phase of acetonitrile-ammonium formate (10mM, pH 4.5) (50:50, v/v). The analytes was detected using an electrospray ionization tandem mass spectrometry in the multiple-reaction-monitoring mode. The standard curve was linear (r=0.998) over the concentration range of 2.0-200 ng/ml. The intra- and inter-assay coefficients of variation ranged from 2.8 to 7.8 and 6.7 to 8.9%, respectively. The recoveries of tiropramide ranged from 50.2 to 53.1%, with that of cisapride (internal standard) being 60.9+/-5.3%. The lower limit of quantification for tiropramide was 2.0 ng/ml using 100 microl plasma sample. This method was applied to the pharmacokinetic study of tiropramide in human.

  9. Ultrahigh-Performance Liquid Chromatography (UHPLC)-Tandem Mass Spectrometry (MS/MS) Quantification of Nine Target Indoles in Sparkling Wines.

    PubMed

    Tudela, Rebeca; Ribas-Agustí, Albert; Buxaderas, Susana; Riu-Aumatell, Montserrat; Castellari, Massimo; López-Tamames, Elvira

    2016-06-15

    An ultrahigh-performance liquid chromatography (UHPLC)-tandem mass spectrometry (MS/MS) method was developed for the simultaneous determination of nine target indoles in sparkling wines. The proposed method requires minimal sample pretreatment, and its performance parameters (accuracy, repeatability, LOD, and matrix effect) indicate that it is suitable for routine analysis. Four indoles were found at detectable levels in commercial Cava samples: 5-methoxytryptophol (5MTL), tryptophan (TRP), tryptophan ethyl ester (TEE), and N-acetylserotonin (NSER). Two of them, NSER and 5MTL, are reported here for the first time in sparkling wines, with values of 0.3-2 and 0.29-29.2 μg/L, respectively. In the same samples, the contents of melatonin (MEL), serotonin (SER), 5-hydroxytryptophan (5-OHTRP), 5-hydroxyindole-3-acetic acid (5OHIA), and 5-methoxy-3-indoleacetic acid (5MIA) were all below the corresponding limits of detection.

  10. Direct and sensitive determination of glyphosate and aminomethylphosphonic acid in environmental water samples by high performance liquid chromatography coupled to electrospray tandem mass spectrometry.

    PubMed

    Guo, Hongyue; Riter, Leah S; Wujcik, Chad E; Armstrong, Daniel W

    2016-04-22

    A novel method based on high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS) was developed for the sensitive determination of glyphosate and its major degradation product, AMPA in environmental water samples. The method involves the use of MS compatible mobile phases (0.1% formic acid in water and acetonitrile) for HPLC and direct analysis of water samples without sample derivatization. The method has been validated in different types of water matrices (drinking, surface and groundwater) by accuracy and precision studies with samples spiked at 0.1, 7.5 and 90 ppb. All mean accuracy values ranged from 85% to 112% for glyphosate and AMPA using both primary and secondary quantitative ion transitions (RSD ≤ 10%). Moreover, both primary and secondary ion transitions for glyphosate and AMPA can achieve the quantitation limits at 0.1 ppb. The linear dynamic range of the calibration curves were from 0.1 to 100 ppb for each analyte at each ion transitions with correlation coefficient higher than 0.997. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Rapid quantitative analysis of individual anthocyanin content based on high-performance liquid chromatography with diode array detection with the pH differential method.

    PubMed

    Wang, Huayin

    2014-09-01

    A new quantitative technique for the simultaneous quantification of the individual anthocyanins based on the pH differential method and high-performance liquid chromatography with diode array detection is proposed in this paper. The six individual anthocyanins (cyanidin 3-glucoside, cyanidin 3-rutinoside, petunidin 3-glucoside, petunidin 3-rutinoside, and malvidin 3-rutinoside) from mulberry (Morus rubra) and Liriope platyphylla were used for demonstration and validation. The elution of anthocyanins was performed using a C18 column with stepwise gradient elution and individual anthocyanins were identified by high-performance liquid chromatography with tandem mass spectrometry. Based on the pH differential method, the high-performance liquid chromatography peak areas of maximum and reference absorption wavelengths of anthocyanin extracts were conducted to quantify individual anthocyanins. The calibration curves for these anthocyanins were linear within the range of 10-5500 mg/L. The correlation coefficients (r(2)) all exceeded 0.9972, and the limits of detection were in the range of 1-4 mg/L at a signal-to-noise ratio ≥5 for these anthocyanins. The proposed quantitative analysis was reproducible with good accuracy of all individual anthocyanins ranging from 96.3 to 104.2% and relative recoveries were in the range 98.4-103.2%. The proposed technique is performed without anthocyanin standards and is a simple, rapid, accurate, and economical method to determine individual anthocyanin contents. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Liquid Chromatography-Tandem Mass Spectrometry: An Emerging Technology in the Toxicology Laboratory.

    PubMed

    Zhang, Yan Victoria; Wei, Bin; Zhu, Yu; Zhang, Yanhua; Bluth, Martin H

    2016-12-01

    In the last decade, liquid chromatography-tandem mass spectrometry (LC-MS/MS) has seen enormous growth in routine toxicology laboratories. LC-MS/MS offers significant advantages over other traditional testing, such as immunoassay and gas chromatography-mass spectrometry methodologies. Major strengths of LC-MS/MS include improvement in specificity, flexibility, and sample throughput when compared with other technologies. Here, the basic principles of LC-MS/MS technology are reviewed, followed by advantages and disadvantages of this technology compared with other traditional techniques. In addition, toxicology applications of LC-MS/MS for simultaneous detection of large panels of analytes are presented. Copyright © 2016 Elsevier Inc. All rights reserved.

  13. High Performance Liquid Chromatography Experiments to Undergraduate Laboratories

    ERIC Educational Resources Information Center

    Kissinger, Peter T.; And Others

    1977-01-01

    Reviews the principles of liquid chromatography with electrochemical detection (LCEC), an analytical technique that incorporates the advantages of both liquids chromatography and electrochemistry. Also suggests laboratory experiments using this technique. (MLH)

  14. Profiling the indole alkaloids in yohimbe bark with ultra-performance liquid chromatography coupled with ion mobility quadrupole time-of-flight mass spectrometry.

    PubMed

    Sun, Jianghao; Baker, Andrew; Chen, Pei

    2011-09-30

    An ultra-performance liquid chromatography/ion mobility quadrupole time-of-flight mass spectrometry (UPLC/IM-QTOF-MS) method was developed for profiling the indole alkaloids in yohimbe bark. Many indole alkaloids with the yohimbine or ajmalicine core structure, plus methylated, oxidized and reduced species, were characterized. Common fragments and mass differences are described. It was shown that the use of IMS could provide another molecular descriptor, i.e. molecular shape by rotationally averaged collision cross-section; this is of great value for identification of constituents when reference materials are usually not available. Using the combination of high resolution (~40000) accurate mass measurement with time-aligned parallel (TAP) fragmentation, MS(E) (where E represents collision energy), ion mobility mass spectrometry (IMS) and UPLC chromatography, a total 55 indole alkaloids were characterized and a few new indole alkaloids are reported for the first time. Published in 2011 by John Wiley & Sons, Ltd.

  15. Determination of rivaroxaban in patient's plasma samples by anti-Xa chromogenic test associated to High Performance Liquid Chromatography tandem Mass Spectrometry (HPLC-MS/MS).

    PubMed

    Derogis, Priscilla Bento Matos; Sanches, Livia Rentas; de Aranda, Valdir Fernandes; Colombini, Marjorie Paris; Mangueira, Cristóvão Luis Pitangueira; Katz, Marcelo; Faulhaber, Adriana Caschera Leme; Mendes, Claudio Ernesto Albers; Ferreira, Carlos Eduardo Dos Santos; França, Carolina Nunes; Guerra, João Carlos de Campos

    2017-01-01

    Rivaroxaban is an oral direct factor Xa inhibitor, therapeutically indicated in the treatment of thromboembolic diseases. As other new oral anticoagulants, routine monitoring of rivaroxaban is not necessary, but important in some clinical circumstances. In our study a high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was validated to measure rivaroxaban plasmatic concentration. Our method used a simple sample preparation, protein precipitation, and a fast chromatographic run. It was developed a precise and accurate method, with a linear range from 2 to 500 ng/mL, and a lower limit of quantification of 4 pg on column. The new method was compared to a reference method (anti-factor Xa activity) and both presented a good correlation (r = 0.98, p < 0.001). In addition, we validated hemolytic, icteric or lipemic plasma samples for rivaroxaban measurement by HPLC-MS/MS without interferences. The chromogenic and HPLC-MS/MS methods were highly correlated and should be used as clinical tools for drug monitoring. The method was applied successfully in a group of 49 real-life patients, which allowed an accurate determination of rivaroxaban in peak and trough levels.

  16. Structural Characterisation of Acetogenins from Annona muricata by Supercritical Fluid Chromatography Coupled to High-Resolution Tandem Mass Spectrometry.

    PubMed

    Laboureur, Laurent; Bonneau, Natacha; Champy, Pierre; Brunelle, Alain; Touboul, David

    2017-11-01

    Acetogenins are plant polyketides known to be cytotoxic and proposed as antitumor candidates. They are also suspected to be alimentary neurotoxins. Their occurrence as complex mixtures renders their dereplication and structural identification difficult using liquid chromatography coupled to tandem mass spectrometry and efforts are required to improve the methodology. To develop a supercritical fluid chromatography (SFC) high-resolution tandem mass spectrometry method, involving lithium post-column cationisation, for the structural characterisation of Annonaceous acetogenins in crude extracts. The seeds of Annona muricata L. were extracted with methanol. Supercritical fluid chromatography of the extract, using a 2-ethylpyridine stationary phase column, was monitored using a high-resolution quadrupole time-of-flight mass spectrometer. Lithium iodide was added post-column in the make-up solvent. For comparison, the same extract was analysed using high-pressure liquid chromatography coupled to the same mass spectrometer, with a column based on solid core particles. Sensitivity was similar for both HPLC and SFC approaches. Retention behaviour and fragmentation pathways of three different isomer groups are described. A previously unknown group of acetogenins was also evidenced for the first time. The use of SFC-MS/MS allows the reduction of the time of analysis, of environmental impact and an increase in the chromatographic resolution, compared to liquid chromatography. This new methodology enlightened a new group of acetogenins, isomers of montanacin-D. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  17. Versatile lipid profiling by liquid chromatography-high resolution mass spectrometry using all ion fragmentation and polarity switching. Preliminary application for serum samples phenotyping related to canine mammary cancer.

    PubMed

    Gallart-Ayala, H; Courant, F; Severe, S; Antignac, J-P; Morio, F; Abadie, J; Le Bizec, B

    2013-09-24

    Lipids represent an extended class of substances characterized by such high variety and complexity that makes their unified analyses by liquid chromatography coupled to either high resolution or tandem mass spectrometry (LC-HRMS or LC-MS/MS) a real challenge. In the present study, a new versatile methodology associating ultra high performance liquid chromatography coupled to high resolution tandem mass spectrometry (UHPLC-HRMS/MS) have been developed for a comprehensive analysis of lipids. The use of polarity switching and "all ion fragmentation" (AIF) have been two action levels particularly exploited to finally permit the detection and identification of a multi-class and multi-analyte extended range of lipids in a single run. For identification purposes, both higher energy collision dissociation (HCD) and in-source CID (collision induced dissociation) fragmentation were evaluated in order to obtain information about the precursor and product ions in the same spectra. This approach provides both class-specific and lipid-specific fragments, enhancing lipid identification. Finally, the developed method was applied for differential phenotyping of serum samples collected from pet dogs developing spontaneous malignant mammary tumors and health controls. A biological signature associated with the presence of cancer was then successfully revealed from this lipidome analysis, which required to be further investigated and confirmed at larger scale. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Metabolic profiling of the hepatotoxicity and nephrotoxicity of Ginkgolic acids in rats using ultra-performance liquid chromatography-high-definition mass spectrometry.

    PubMed

    Qian, Yiyun; Peng, Yunru; Shang, Erxin; Zhao, Ming; Yan, Liang; Zhu, Zhenhua; Tao, Jinhua; Su, Shulan; Guo, Sheng; Duan, Jin-Ao

    2017-08-01

    Ginkgolic acids (GAs) are thought to be the potentially hazardous constituents corresponding to the toxic side effects of Ginkgo products. In this study, toxicological and metabolomics studies of GAs were carried out by ultra-performance liquid chromatography-high-definition mass spectrometry (UPLC-HDMS). Significant changes in serum clinical chemistry were observed in the both low (100 mg/kg) and high (900 mg/kg) doses. Especially the serum enzyme of ALT, AST, LDH, and CK decreased in treated groups. The histopathological observation demonstrated hepatic steatosis in liver and tubular vacuolar degeneration in kidney. These results demonstrated the hepatotoxicity and nephrotoxicity of GAs. Functional disorders are more likely to be toxic induced by GAs. Metabolic profiling within seven days revealed the change of the body status after oral administration. The results indicated the body function was significantly influenced at the 3rd day and could recover in seven days. Metabolomic analysis showed alterations in 14 metabolites from plasma such as LysoPC(18:0), LysoPC(18:2) and other lipids. The results suggested that exposure to GAs could cause disturbances in liver and kidney function associated with the metabolisms of lipids, glucose and the enzyme activity. Copyright © 2017. Published by Elsevier B.V.

  19. A high performance liquid chromatography tandem mass spectrometry for the quantification of tacrolimus in human bile in liver transplant recipients.

    PubMed

    Tron, Camille; Rayar, Michel; Petitcollin, Antoine; Beaurepaire, Jean-Marie; Cusumano, Caterina; Verdier, Marie-Clémence; Houssel-Debry, Pauline; Camus, Christophe; Boudjema, Karim; Bellissant, Eric; Lemaitre, Florian

    2016-12-02

    Tacrolimus whole-blood concentrations imperfectly reflect concentrations at the effect site. Tacrolimus concentrations in the transplanted organ could be more relevant to predict rejection events. Because liver biopsy cannot be repeatedly performed after liver transplantation, we suggested measuring tacrolimus in the bile to have a cost-effective and clinically implementable surrogate marker of intra-hepatic tacrolimus concentration. We developed and fully validated a liquid chromatography-tandem mass spectrometry method for the determination of tacrolimus in human bile. Sample purification was achieved using protein precipitation and liquid-liquid extraction with ethyl-acetate. Gradient elution was performed using a C18 analytical column with a 5min run-time. The method was linear from 0.5ng/mL to 20ng/mL. In this concentration range, within-day and between-day precisions as well as overall bias were within ±15%. Matrix effect was fully corrected by the internal standard (ascomycin). The assay was optimized to achieve good selectivity in this complex biological matrix. Tacrolimus was found to be stable in bile stored 6 months at -80°C, after 3 freeze and thaw cycles, 20h at room temperature and 24h in extracts kept at 15°C in the auto-sampler. The method was applied to quantify tacrolimus in bile from liver transplant recipients. It allowed getting preliminary data about tacrolimus excretion profile in bile and showed the lack of correlation between tacrolimus whole blood concentration and tacrolimus liver exposition. This alternative and innovative analytical approach of tacrolimus bio-analysis appears suitable for further studies evaluating relevance of biliary tacrolimus concentration as a new pharmacological marker of immunosuppressive activity. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Chromatographic behavior of small organic compounds in low-temperature high-performance liquid chromatography using liquid carbon dioxide as the mobile phase.

    PubMed

    Motono, Tomohiro; Nagai, Takashi; Kitagawa, Shinya; Ohtani, Hajime

    2015-07-01

    Low-temperature high-performance liquid chromatography, in which a loop injector, column, and detection cell were refrigerated at -35ºC, using liquid carbon dioxide as the mobile phase was developed. Small organic compounds (polyaromatic hydrocarbons, alkylbenzenes, and quinones) were separated by low-temperature high-performance liquid chromatography at temperatures from -35 to -5ºC. The combination of liquid carbon dioxide mobile phase with an octadecyl-silica (C18 ) column provided reversed phase mode separation, and a bare silica-gel column resulted in normal phase mode separation. In both the cases, nonlinear behavior at approximately -15ºC was found in the relationship between the temperature and the retention factors of the analytes (van't Hoff plots). In contrast to general trends in high-performance liquid chromatography, the decrease in temperature enhanced the separation efficiency of both the columns. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Coupling nanoliter high-performance liquid chromatography to inductively coupled plasma mass spectrometry for arsenic speciation.

    PubMed

    Cheng, Heyong; Shen, Lihuan; Liu, Jinhua; Xu, Zigang; Wang, Yuanchao

    2018-04-01

    Nanoliter high-performance liquid chromatography shows low consumption of solvents and samples, offering one of the best choices for arsenic speciation in precious samples in combination with inuctively coupled plasma mass spectrometry. A systematic investigation on coupling nanoliter high-performance liquid chromatography to inductively coupled plasma mass spectrometry from instrument design to injected sample volume and mobile phase was performed in this study. Nanoflow mobile phase was delivered by flow splitting using a conventional high-pressure pump with reuse of mobile phase waste. Dead volume was minimized to 60 nL for the sheathless interface based on the previously developed nanonebulizer. Capillary columns for nanoliter high-performance liquid chromatography were found to be sensitive to sample loading volume. An apparent difference was also found between the mobile phases for nanoliter and conventional high-performance liquid chromatography. Baseline separation of arsenite, arsenate, monomethylarsenic, and dimethylarsenic was achieved within 11 min on a 15 cm C 18 capillary column and within 12 min on a 25 cm strong anion exchange column. Detection limits of 0.9-1.8 μg/L were obtained with precisions variable in the range of 1.6-4.2%. A good agreement between determined and certified values of a certified reference material of human urine (GBW 09115) validated its accuracy along with good recoveries (87-102%). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Rapid separation and identification of phenolics in crude red grape skin extracts by high performance liquid chromatography coupled to diode array detection and tandem mass spectrometry.

    PubMed

    Ji, Mei; Li, Chen; Li, Qiang

    2015-10-02

    A rapid and efficient method was established for the simultaneous determination of structures and configurations for 45 phenolics isolated from crude red grape skin extracts without extensive sample preparation. Separation and compound assignments were achieved using high performance liquid chromatography coupled to diode array detection and tandem mass spectrometry (HPLC-DAD-MS(2)). A Poroshell 120 EC-C18 (100mm×3.0mm, 2.7μm) column was employed to separate the phenolics, which were eluted using a gradient of acetonitrile and water acidified with 0.2% formic acid. Phenolics were identified by comparison of their UV-vis spectra, mass spectra and MS(2) data with those in the literature. Using this procedure, five compounds were detected for the first time in Vitis amurensis. Good separation of most phenolics was achieved in 26min. The methods described here can be used for the characterization of phenolics in a variety of grapes and grape products. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Development of Extraction Methods for the Analysis of Perfluorinated Compounds in Leather with High Performance Liquid Chromatography Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zhang, Yan; Wang, Youchao; Tang, Chuanjiang; Nie, Jingmei; Xu, Chengtao

    2018-01-01

    Perfluorinated compounds (PFCs), used to provide water, oil, grease, heat and stain repellency to a range of textile and other products, have been found to be persistent in the environment and are associated with adverse effects on humans and wildlife. This study presents the development and validation of an analytical method to determine the simultaneous presence of eleven PFCs in leather using solid-phase extraction followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The perfluorinated compounds were primarily extracted from the samples by a liquid extraction procedure by ultrasonic, in which the parameters were optimized. Then the solid-phase extraction (SPE) is the most important advantages of the developed methodology. The sample volume and elution conditions were optimized by means of an experimental design. The proposed method was applied to determine the PFCs in leather, where the detection limits of the eleven compounds were 0.09-0.96 ng/L, and the recoveries of all compounds spiked at 5 ng/L concentration level were in the range of 65-96%, with a better RSD lower than 19% (n = 7).

  4. Determination of ten monohydroxylated polycyclic aromatic hydrocarbons by liquid-liquid extraction and liquid chromatography/tandem mass spectrometry.

    PubMed

    Fan, Ruifang; Ramage, Robert; Wang, Dongli; Zhou, Junqiang; She, Jianwen

    2012-05-15

    The aim of this study is to develop and validate an analytical method for the quantitation of ten urinary monohydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) through high pressure liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). After enzymatic deconjugation, urine samples were extracted by liquid-liquid extraction (LLE) and OH-PAHs were analyzed by HPLC/MS/MS operated in negative electrospray ionization (ESI) and multiple reaction monitoring (MRM) mode. LLE was conducted with the solvent mixture of pentane and toluene, which reduced the matrix interferences and enhanced the method sensitivity significantly. Deuterated and (13)C-labeled analogs are used as internal standards. Calibration curves of all target analytes shows favorable linearity within the concentration range of 5.9-15,000.0 ng/L for different OH-PAHs with the regression coefficients above 0.993. The limits of detection (LODs) in pooled urine ranged from 1.72 to 17.47 ng/L, which were much lower than those obtained by a gas chromatography/high resolution mass spectrometry (GC/HRMS) method. The method shows satisfactory accuracy and precision when analyzing three different levels of OH-PAHs spiked in pooled urine. Except for 1-hydroxynaphthalene, recoveries of other OH-PAHs were in the range of 100 ± 20% with a variation coefficient of less than 13%. The measurement of OH-PAHs from a QC sample of the Centers for Disease Control and Prevention (CDC) generated results close to the values measured by CDC. This method has been successfully employed in the California Biomonitoring Program. Published by Elsevier B.V.

  5. Multiresidue pesticide analysis of tuber and root commodities by QuEchERS extraction and ultra-performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Garrido Frenich, Antonia; Martín Fernández, María del Mar; Díaz Moreno, Laura; Martínez Vidal, Jose Lúis; López-Gutiérrez, Noelia

    2012-01-01

    A simple, rapid, and reliable multiresidue method to determine 84 pesticides in potato and carrot samples by ultra-performance liquid chromatography coupled to MS/MS has been developed and fully validated for routine analysis according to ISO/IEC 17025:2005. The method makes use of a buffered Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) sample preparation procedure based on a single extraction with acidified acetonitrile, followed by partitioning with salts. Chromatographic conditions were optimized in order to achieve a rapid separation in the multiple reaction monitoring mode. Performance characteristics of the method, including an estimation of measurement uncertainty using validation data, are reported for both matrixes. Calibration curves were linear from 0.010 to 0.150 mg/kg for most compounds. The LOD and LOQ were 0.006 and 0.010 mg/kg, respectively, except for fluorocloridone, fluquinconazol, and hexitiazox, which were 0.030 and 0.050 mg/kg, respectively. Recoveries obtained were in the range 70-116%, with intraday precision values < or = 20% RSD and interday precision values < or = 25% RSD at two different concentration levels. The overall uncertainty of the method was estimated at two concentrations as being lower than 34% in all cases. The method has been applied to the analysis of 70 vegetable samples, and imidacloprid and linuron were the pesticides most frequently found in potato and carrot commodities, respectively.

  6. Highly sensitive reversed-phase high-performance liquid chromatography assay for the detection of Tamm-Horsfall protein in human urine.

    PubMed

    Akimoto, Masaru; Hokazono, Eisaku; Ota, Eri; Tateishi, Takiko; Kayamori, Yuzo

    2016-01-01

    Tamm-Horsfall protein (also known as uromodulin) is the most abundant urinary protein in healthy individuals. Since initially characterized by Tamm and Horsfall, the amount of urinary excretion and structural mutations of Tamm-Horsfall protein is associated with kidney diseases. However, currently available assays for Tamm-Horsfall protein, which are mainly enzyme-linked immunosorbent assay-based, suffer from poor reproducibility and might give false negative results. We developed a novel, quantitative assay for Tamm-Horsfall protein using reversed-phase high-performance liquid chromatography. A precipitation pretreatment avoided urine matrix interference and excessive sample dilution. High-performance liquid chromatography optimization based on polarity allowed excellent separation of Tamm-Horsfall protein from other major urine components. Our method exhibited high precision (based on the relative standard deviations of intraday [≤2.77%] and interday [≤5.35%] repetitions). The Tamm-Horsfall protein recovery rate was 100.0-104.2%. The mean Tamm-Horsfall protein concentration in 25 healthy individuals was 31.6 ± 18.8 mg/g creatinine. There was a strong correlation between data obtained by high-performance liquid chromatography and enzyme-linked immunosorbent assay (r = 0.906), but enzyme-linked immunosorbent assay values tended to be lower than high-performance liquid chromatography values at low Tamm-Horsfall protein concentrations. The high sensitivity and reproducibility of our Tamm-Horsfall protein assay will reduce the number of false negative results of the sample compared with enzyme-linked immunosorbent assay. Moreover, our method is superior to other high-performance liquid chromatography methods, and a simple protocol will facilitate further research on the physiological role of Tamm-Horsfall protein. © The Author(s) 2015.

  7. Ultrasound/microwave-assisted solid-liquid-solid dispersive extraction with high-performance liquid chromatography coupled to tandem mass spectrometry for the determination of neonicotinoid insecticides in Dendrobium officinale.

    PubMed

    Zheng, Shuilian; Wu, Huizhen; Li, Zuguang; Wang, Jianmei; Zhang, Hu; Qian, Mingrong

    2015-01-01

    A one-step ultrasound/microwave-assisted solid-liquid-solid dispersive extraction procedure was used for the simultaneous determination of eight neonicotinoids (dinotefuran, nitenpyram, thiamethoxam, clothianidin, imidacloprid, acetamiprid, thiacloprid, imidaclothiz) in dried Dendrobium officinale by liquid chromatography combined with electrospray ionization triple quadrupole tandem mass spectrometry in multiple reaction monitoring mode. The samples were quickly extracted by acetonitrile and cleaned up by the mixed dispersing sorbents including primary secondary amine, C18 , and carbon-GCB. Parameters that could influence the ultrasound/microwave-assisted extraction efficiency such as microwave irradiation power, ultrasound irradiation power, temperature, and solvent were investigated. Recovery studies were performing well (70.4-113.7%) at three examined spiking levels (10, 50, and 100 μg/kg). Meanwhile, the limits of quantification for the neonicotinoids ranged from 0.87 to 1.92 μg/kg. The method showed good linearity in the concentration range of 1-100 μg/L with correlation coefficients >0.99. This quick and useful analytical method could provide a basis for monitoring neonicotinoid insecticide residues in herbs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Determination of pyrethrin and pyrethroid residues in animal fat using liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Moloney, M; Tuck, S; Ramkumar, A; Furey, A; Danaher, M

    2018-03-01

    A method was developed for the confirmatory and quantitative analysis of one pyrethrin and 18 pyrethroid residues in animal fat. Fat was extracted was collected from adipose tissue melted in an oven at 65 °C for 2 h. Fat samples (1 g) were dispersed with deactivated Florisil ® sorbent and extracted with MeCN. Sample extracts were purified by cold temperature precipitation at -30 °C for 4 h and further purified using dispersive solid-phase extraction (d-SPE) clean-up in tubes containing 500 mg of Z-SEP+ and 125 mg of PSA bonded silica. Purified samples were analysed by ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) detection. Chromatographic separation was carried out on a Acquity C 8 BEH column, using a binary gradient separation comprising of mobile phase A, 5 mM ammonium formate in water:MeOH (80:20, v/v,) and mobile phase B, 5 mM ammonium formate in MeOH. The mass spectrometer was operated in the positive electrospray ionisation mode (ESI(+)). Validation was performed following the 2002/657/EC guidelines. Trueness ranged between 84% and 143% and precision ranged between 3.9% and 29%. The developed method is particularly advantageous because the sample preparation procedure does not require complex sample extraction equipment and uses less solvent compared to other sample preparation protocols. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Quantification of patulin in fruit leathers by ultra-high-performance liquid chromatography-photodiode array (UPLC-PDA).

    PubMed

    Maragos, Chris M; Busman, Mark; Ma, Liang; Bobell, John

    2015-01-01

    Patulin is a mycotoxin commonly found in certain fruit and fruit products. For this reason many countries have established regulatory limits pertaining to, in particular, apple juice and apple products. Fruit leathers are produced by dehydrating fruit puree, leaving a sweet product that has a leathery texture. A recent report in the literature described the detection of patulin at substantial levels in fruit leathers. To investigate this further, an ultra-high-performance liquid chromatography-photodiode array (UPLC-PDA) method was developed for the sensitive detection of patulin in fruit leathers. Investigations were also made of the suitability of direct analysis in real time-mass spectrometry (DART-MS) for detection of patulin from the surface of fruit leathers. Results indicated DART-MS was insufficiently sensitive for quantification from the surface of home-style apple leathers, although patulin spiked onto the surface of leather or peel could be detected. The UPLC-PDA method was used to determine the fate of patulin during the preparation of home-made fruit leathers. Interestingly, when a home-style process was used, the patulin was not destroyed, but rather increased in concentration as the puree was dehydrated. The UPLC-PDA method was also used to screen for patulin in commercial fruit leathers. Of the 36 products tested, 14 were above the limit of detection (3.5 μg kg(-1)) and nine were above the limit of quantification (12 μg kg(-1)). Positive samples were confirmed by UPLC-MS/MS. Only one sample was found above the US regulatory limit for single-strength apple juice products (50 μg kg(-1)). These results suggest patulin can be concentrated during preparation and can be found in fruit leathers. The limited survey suggests that patulin is fairly prevalent in such commercial products, but that the levels are usually low.

  10. Simultaneous quantitative determination of bioactive terpene indole alkaloids in ethanolic extracts of Catharanthus roseus (L.) G. Don by ultra high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Kumar, Sunil; Singh, Awantika; Kumar, Brijesh; Singh, Bikarma; Bahadur, Lal; Lal, Mohan

    2018-03-20

    A rapid, sensitive and reproducible method using ultra-high-performance liquid chromatography coupled with electrospray ionization hybrid triple quadrupole-linear ion trap mass spectrometry (UHPLC-ESI-QqQ LIT -MS/MS) in multiple reaction monitoring (MRM) mode was developed and validated for simultaneous quantitation of anticancer (vincristine, vinblastine, vindesine), antihypertensive (ajmaline, ajmalicine, reserpine), aphrodisiac (yohimbine), sedative (serpentine) agents, dietary supplement (vinpocetine, yohimbine) and precursor of vinblastine (vindoline) from crude extracts of Catharanthus roseus. The precursor to product ion transitions for these compounds were observed at m/z 327 → 144, 355 → 144, 754 → 355, 353 → 144, 349 → 317, 825 → 225, 811 → 224, 458 → 188, 351 → 280 and 609 → 195, respectively in positive ionization mode. Chromatographic separation of all targeted TIAs was performed on ACQUITY UPLC BEH™ C 18 column (1.7 μm, 2.1 mm × 50 mm). The calibration curves were linear within the concentration range 0.5-1000 ng/mL and correlation coefficients (R 2 ) were closer to 1. Limit of detection (LOD) and limit of quantitation (LOQ) ranged from 0.039-0.583 ng/mL and 0.118-1.767 ng/mL, respectively. The intra-day (0.23-2.71% RSD) and inter-day (0.40-2.90% RSD) precision, stability (0.69-3.45% RSD) and recovery (99.63-104.30% ± %RSD ≤ 3.03%) were acceptable indicating good accuracy of the developed method. The method was successfully applied in ethanolic extracts of 39 samples of C. roseus parts (leaf, stem and root) collected from five different locations in India. Serpentine was detected as one of the most abundant TIA. Principal component analysis (PCA) was able to successfully discriminate among C. roseus samples on the basis of content of targeted TIAs. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Quality control of modified xiaoyao san through the determination of 22 active components by ultra-performance liquid chromatography.

    PubMed

    Qin, Feng; Huang, Jun; Qiu, Xinjian; Hu, Sihang; Huang, Xi

    2011-01-01

    A simple, sensitive, and reliable ultra-performance liquid chromatography (UPLC) method has been developed for simultaneous determination of 22 major constituents in modified xiaoyao san (MXS), a multiherbal formula. The chromatographic separation was performed on an ACQUITY UPLC BEH C18 column (150 x 2.1 mm, 1.7 microm, particle size), with an aqueous 0.5% acetic acid and acetonitrile mobile phase gradient. The method was validated for linearity (r2 >0.9937), intraday and interday precision (RSD <8.51%), recovery (91.18-107.73%), LOD (0.02-4.17 ng/mL), and LOQ (0.05-12.50 ng/mL). The established method was successfully applied to quantify the 22 marker compounds in MXS, which provided a useful basis of overall evaluation of the quality of MXS.

  12. Alkaloid profiling of the traditional Chinese medicine Rhizoma corydalis using high performance liquid chromatography-tandem quadrupole time-of-flight mass spectrometry

    PubMed Central

    Sun, Mingqian; Liu, Jianxun; Lin, Chengren; Miao, Lan; Lin, Li

    2014-01-01

    Since alkaloids are the major active constituents of Rhizoma corydalis (RC), a convenient and accurate analytical method is needed for their identification and characterization. Here we report a method to profile the alkaloids in RC based on liquid chromatography-tandem quadrupole time-of-flight mass spectrometry (LC–Q-TOF-MS/MS). A total of 16 alkaloids belonging to four different classes were identified by comparison with authentic standards. The fragmentation pathway of each class of alkaloid was clarified and their differences were elucidated. Furthermore, based on an analysis of fragmentation pathways and alkaloid profiling, a rapid and accurate method for the identification of unknown alkaloids in RC is proposed. The method could also be useful for the quality control of RC. PMID:26579385

  13. Distribution of C16:0, C18:0, C24:1, and C24:0 sulfatides in central nervous system lipid rafts by quantitative ultra-high-pressure liquid chromatography tandem mass spectrometry.

    PubMed

    Moyano, Ana Lis; Li, Guannan; Lopez-Rosas, Aurora; Månsson, Jan-Eric; van Breemen, Richard B; Givogri, Maria Irene

    2014-12-15

    Sulfated galactosylceramides (sulfatides) are glycosphingolipids associated with cholesterol- and sphingolipid-enriched membrane microdomains (lipid rafts) and are highly expressed in brain tissue. Although it is known that sulfatide species show heterogeneity in their fatty acid acyl group composition throughout brain development, their lipid raft distribution and biological relevance is poorly understood. We validated a fast and sensitive ultra-high-pressure liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method to measure developmentally regulated sulfatide species (C16:0, C18:0, C24:1, and C24:0) in central nervous system (CNS) lipid rafts isolated without using detergent. Our UHPLC-MS/MS assay showed good accuracy and precision with a linear range of 5 to 1,000 nM for C18:0 and C24:1 sulfatides and 10 to 1,000 nM for C16:0 and C24:0 sulfatides. We applied this quantitative analysis to detergent-free lipid rafts isolated from wild-type mice and arylsulfatase A-deficient (ASA knockout) mice that accumulate sulfatides. All four sulfatide species were more abundant in raft membranes than in non-raft membranes, with a significant increase in lipid rafts isolated from ASA knockout mice. This is the first description of an analytical method to study these sulfatide species in raft and non-raft membranes and has the potential to be applied to preparations from other tissues. Copyright © 2014 Elsevier Inc. All rights reserved.

  14. Broad-spectrum immunoaffinity cleanup for the determination of aflatoxins B1, B2, G1, G2, M1, M2 in Ophiocordyceps sinensis and its pharmaceutical preparations by ultra performance liquid chromatography tandem mass spectrometry.

    PubMed

    Sun, Shujuan; Xie, Jie; Peng, Tao; Shao, Bing; Zhu, Kui; Sun, Yuanze; Yao, Kai; Gu, Qiang; Zhang, Jing; Fan, Chunlin; Chen, Ying; Jiang, Haiyang

    2017-11-15

    An ultra performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method was developed and validated for the simultaneous determination of aflatoxins B 1 , B 2 , G 1 , G 2 , M 1 and M 2 (AFB 1 , AFB 2 , AFG 1 , AFG 2 , AFM 1 and AFM 2 ) in Ophiocordyceps sinensis and its pharmaceutical preparations. A rapid and reliable immunoaffinity column containing a broad-spectrum monoclonal antibody for six aflatoxins was used for sample cleanup. Under the optimized conditions, the home-made immunoaffinity column capacity were about 315, 319, 292, 102, 444 and 369ng/mL gel for AFB 1 , AFB 2 , AFG 1 , AFG 2 , AFM 1 and AFM 2 , respectively. Recoveries for all tested aflatoxins ranged from 79.28% to 103.42% with relative standard deviation less than 8%. The limits of quantitation were in the range of 0.008-0.045μg/kg. Among 31 real samples analyzed, one sample was contaminated with AFB 1 , AFB 2 and AFM 1 at levels of 0.483, 0.068 and 0.104μg/kg, respectively. The established method is simple, accurate, and can be effectively used to determine the aflatoxins in Ophiocordyceps sinensis and its pharmaceutical preparations. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Characterization and identification of iridoid glucosides, flavonoids and anthraquinones in Hedyotis diffusa by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry.

    PubMed

    Liu, E-Hu; Zhou, Ting; Li, Guo-Bin; Li, Jing; Huang, Xiu-Ning; Pan, Feng; Gao, Ning

    2012-01-01

    The multiple bioactive constituents in Hedyotis diffusa Willd. (H. diffusa) were extracted and characterized by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry (HPLC-ESI-MS(n)). The optimized separation condition was obtained using an Agilent ZorBax SB-C18 column (4.6×150 mm, 5 μm) and gradient elution with water (containing 0.1% formic acid) and acetonitrile (containing 0.1% formic acid), under which baseline separation for the majority of compounds was achieved. Among the compounds detected, 14 iridoid glucosides, 10 flavonoids, 7 anthraquinones, 1 coumarin and 1 triterpene were unambiguously identified or tentatively characterized based on their retention times and mass spectra in comparison with the data from standards or references. The fragmentation behavior for different types of constituents was also investigated, which could contribute to the elucidation of these constituents in H. diffusa. The present study reveals that even more iridoid glycosides were found in H. diffusa than hitherto assumed. The occurrence of two iridoid glucosides and five flavonoids in particular has not yet been described. This paper marks the first report on the structural characterization of chemical compounds in H. diffusa by a developed HPLC-ESI-MS(n) method. Copyright © 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Determination of Organic Impurities in Anthraquinone Color Additives D&C Violet No. 2 and D&C Green No. 6 by Ultra-High Performance Liquid Chromatography.

    PubMed

    Yang, H H Wendy

    2017-01-01

    A new practical and time-saving ultra-high performance liquid chromatography (UHPLC) method has been developed for determining the organic impurities in the anthraquinone color additives D&C Violet No. 2 and D&C Green No. 6. The impurities determined are p-toluidine, 1-hydroxyanthraquinone, 1,4-dihydroxyanthraquinone, and two subsidiary colors. The newly developed UHPLC method uses a 1.7-μ particle size C-18 column, 0.1 M ammonium acetate and acetonitrile as eluents, and photodiode array detection. For the quantification of the impurities, six-point calibration curves were used with correlation coefficients that ranged from 0.9974 to 0.9998. Recoveries of impurities ranged from 99 to 104%. Relative standard deviations ranged from 0.81 to 4.29%. The limits of detection for the impurities ranged from 0.0067% to 0.216%. Samples from sixteen batches of each color additive were analyzed, and the results favorably compared with the results obtained by gravity-elution column chromatography, thin-layer chromatography, and isooctane extraction. Unlike with those other methods, use of the UHPLC method permits all of the impurities to be determined in a single analysis, while also reducing the amount of organic waste and saving time and labor. The method is expected to be implemented by the U.S. Food and Drug Administration for analysis of color additive samples submitted for batch certification.

  17. Investigation of pharmaceuticals in Missouri natural and drinking water using high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Wang, Chuan; Shi, Honglan; Adams, Craig D; Gamagedara, Sanjeewa; Stayton, Isaac; Timmons, Terry; Ma, Yinfa

    2011-02-01

    A comprehensive method has been developed and validated in two different water matrices for the analysis of 16 pharmaceutical compounds using solid phase extraction (SPE) of water samples, followed by liquid chromatography coupled with tandem mass spectrometry. These 16 compounds include antibiotics, hormones, analgesics, stimulants, antiepileptics, and X-ray contrast media. Method detection limits (MDLs) that were determined in both reagent water and municipal tap water ranged from 0.1 to 9.9 ng/L. Recoveries for most of the compounds were comparable to those obtained using U.S. EPA methods. Treated and untreated water samples were collected from 31 different water treatment facilities across Missouri, in both winter and summer seasons, and analyzed to assess the 16 pharmaceutical compounds. The results showed that the highest pharmaceutical concentrations in untreated water were caffeine, ibuprofen, and acetaminophen, at concentrations of 224, 77.2, and 70 ng/L, respectively. Concentrations of pharmaceuticals were generally higher during the winter months, as compared to those in the summer due, presumably, to smaller water quantities in the winter, even though pharmaceutical loadings into the receiving waters were similar for both seasons. © 2010 Elsevier Ltd. All rights reserved.

  18. [Simultaneous determination of 6 pesticides in drinking water by high performance liquid chromatography-tandem mass spectrometry with solid phase extraction].

    PubMed

    Liu, Hua-liang; Wang, Lian-hong

    2013-05-01

    To develop an analytical method for simultaneous determination of 6 pesticides, namely bentazone, 2,4-dichlorophenoxyacetic acid,carbofuran, carbaryl, atrazine and pentachlorophenol, in drinking water by high performance liquid chromatography-tandem mass spectrometry, and thereby to provide a reference to revise the Health Standards for Drinking Water (GB/T 5750-2006). Meanwhile, to evaluate the content of the above 6 pesticides in the drinking water samples supplied by 12 centralized water plants in Jiangsu province. The 10 ml water sample was acidized by hydrochloric acid to pH ≤ 2, and then concentrated by solid phase extraction cartridge and eluted with acetone. The solvent was changed into methanol after drying by nitrogen blow. The target compounds were separated by C18 column using methanol/water as mobile phase, and detected by mass spectrometry with multi-reaction-monitoring(MRM) mode. The repeatability and sensitivity of the assay were evaluated. The drinking water samples from the 12 water plants were then detected. In this experimental method, the minimum detectable concentration were around 0.02-0.41 µg/L, with the recovery rate at 75%-115%, and the RSD between 2% and 10%. Under the experimental condition, there were no pesticides detected in the drinking water samples from the 12 centralized water plants. The method is efficient and environment-friendly, with little discharge of effluent, which could meet the requirement of the drinking water monitor.

  19. [Determination of perfluoroalkyl acids in lamb liver by high performance liquid chromatography- tandem mass spectrometry combined with dispersive solid phase extraction].

    PubMed

    Zhu, Pingping; Yue, Zhenfeng; Zheng, Zongkun; Zhang, Yi; Li, Wenyin; Zhao, Fengjuan; Xiao Chengui; Bai, Runye; Lin, Wei

    2015-05-01

    A method was developed for the determination of 19 perfluoroalkyl acids (PFAs) in lamb liver by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/ MS) combined with dispersive solid phase extraction. The sample was extracted with acidified acetonitrile, and then cleaned-up by a mixture of N-propylethylenediamine (PSA), C18 and graphitized carbon black (GCB) sorbents. The 19 PFAs were analyzed by HPLC-MS/MS with a C18 chromatographic column, adopting the multiple reaction monitoring (MRM) mode with negative electrospray ionization. The effects of the dosages of hydrochloric acid and the sorbents on the recoveries of the 19 PFAs were studied. For accurate quantitative analysis, the isotope internal standard method was used. The calibration curves were linear with the correlation coefficients over 0.998 in the range of 0.05-20 µg/kg for the 19 PFAs. The limits of detection were 0.004-0.111 µg/kg. The limits of quantification were 0.012-0.370 µg/kg. The mean recoveries of the 19 PFAs at spiked levels of 0.5, 1.0, 2.0 µg/kg were in the range from 80% to 128% with the relative standard deviations of 0.31%-11.1%. The developed method is rapid, simple, accurate. It is suitable for the determination of the 19 PFAs in large quantities of lamb liver samples.

  20. Quantitation of 5-Methyltetrahydrofolate in Cerebrospinal Fluid Using Liquid Chromatography-Electrospray Tandem Mass Spectrometry.

    PubMed

    Arning, Erland; Bottiglieri, Teodoro

    2016-01-01

    We describe a simple stable isotope dilution method for accurate and precise measurement of cerebrospinal fluid (CSF) 5-methyltetrahydrofolate (5-MTHF) as a clinical diagnostic test. 5-MTHF is the main biologically active form of folic acid and is involved in regulation of homocysteine and DNA synthesis. Measurement of 5-MTHF in CSF provides diagnostic information regarding diseases affecting folate metabolism within the central nervous system, in particular inborn errors of folate metabolism. Determination of 5-MTHF in CSF (50 μL) was performed utilizing high performance liquid chromatography coupled with electrospray positive ionization tandem mass spectrometry (HPLC-ESI-MS/MS). 5-MTHF in CSF is determined by a 1:2 dilution with internal standard (5-MTHF-(13)C5) and injected directly onto the HPLC-ESI-MS/MS system. Each assay is quantified using a five-point standard curve (25-400 nM) and has an analytical measurement range of 3-1000 nM.