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Sample records for multi-residue sulfonamide method

  1. Development of multi-residue sulfonamide analysis using LC-MS/MS for detection in wastewater and river samples

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A qTOF-LC-MS/MS method was developed for multi-residue analysis of sulfonamides, including sulfathiazole, sulfadiazine, sulfapyridine, sulfamerazine, sulfamethizole, sulfamethazine, sulfachloropydirine, sulfamethoxazole (SMX), sulfadimethoxine, sulfabenzamide, sulfaquinoxaline, and sulfasalazine. Tw...

  2. Development of an UPLC-MS/MS Sulfonamide Multi-residue Method and its Application to Water, Manure Slurry, and Soils from Swine Rearing Facilities

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An analytical method was developed using ultra performance liquid chromatography-triple quadrupole-tandem mass spectrometry (UPLC-TQ-MS/MS) to simultaneously analyze 14 sulfonamides (SA) in six minutes. Despite the rapidity of the assay the system was properly re-equilibrated in this time. No carryo...

  3. Development of an UPLC-MS/MS Sulfonamide Multi-residue Method and It's Application to Water, Manure Slurry, and Soils from Swine Rearing Facilities

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An analytical method was developed using ultra performance liquid chromatography-triple quadrupole-tandem mass spectrophotometry (UPLC-TQ-MS/MS) to simultaneously analyze 14 sulfonamides (SA) in six minutes. The instrumental detection limit based on signal-to-noise ratio (S/N) > 3, was below 1 pg/µL...

  4. Proficiency test on the determination of pesticide residues in grapes with multi-residue methods.

    PubMed

    Dehouck, Pieter; Grimalt, Susana; Dabrio, Marta; Cordeiro, Fernando; Fiamegos, Yiannis; Robouch, Piotr; Fernández-Alba, Amadeo R; de la Calle, Beatriz

    2015-05-22

    This manuscript presents the results of the International Measurement Evaluation Programme 37 (IMEP-37) study, a proficiency test (PT) which was organised to assess the world-wide performance of food control laboratories on the determination of pesticide residues in grapes. This PT supports the implementation of Regulation (EC) No 396/2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin. Eighty-one participants reported results, forty from EU Member States and forty-one from outside the EU. The test item was a grape sample spiked with 20 selected pesticides. The results of the participants were rated with z- and zeta (ζ-) scores in accordance with ISO 13528 and ISO 17043. The standard deviation for the proficiency assessment, σˆ, of this PT was set at 25% for the 20 measured pesticides based on previous experience with similar measurands. The results reported to IMEP-37 showed that the participants performed satisfactorily, ranging from 81% (carbendazim) to 97% (azoxystrobin, penconazole, pyrimethanil) of the participating laboratories. However, only 30% of the participants managed to analyze all pesticides satisfactorily. Overall, the performance of the participants in this PT was good but there is room for improvement in the development of multi-residue methods for the simultaneous analysis of a large number of pesticides with an increased accuracy. PMID:25888097

  5. Guidelines for the validation of qualitative multi-residue methods used to detect pesticides in food.

    PubMed

    Mol, H G J; Reynolds, S L; Fussell, R J; Stajnbaher, D

    2012-08-01

    There is a current trend for many laboratories to develop and use qualitative gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS) based multi-residue methods (MRMs) in order to greatly increase the number of pesticides that they can target. Before these qualitative MRMs can be used for the monitoring of pesticide residues in food, their fitness-for-purpose needs to be established by initial method validation. This paper sets out to assess the performances of two such qualitative MRMs against a set of parameters and criteria that might be suitable for their effective validation. As expected, the ease of detection was often dependent on the particular pesticide/commodity combinations that were targeted, especially at the lowest concentrations tested (0.01 mg/kg). The two examples also clearly demonstrated that the percentage of pesticides detected was dependent on many factors, but particularly on the capabilities of the automated software/library packages and the parameters and threshold settings selected for operation. Another very important consideration was the condition of chromatographic system and detector at the time of analysis. If the system was relatively clean, then the detection rate was much higher than if it had become contaminated over time from previous injections of sample extracts. The parameters and criteria suggested for method validation of qualitative MRMs are aimed at achieving a 95% confidence level of pesticide detection. However, the presence of any pesticide that is 'detected' will need subsequent analysis for quantification and, depending on the qualitative method used, further evidence of identity. PMID:22851355

  6. Multi-residue method for the analysis of 85 current-use and legacy pesticides in bed and suspended sediments

    USGS Publications Warehouse

    Smalling, K.L.; Kuivila, K.M.

    2008-01-01

    A multi-residue method was developed for the simultaneous determination of 85 current-use and legacy organochlorine pesticides in a single sediment sample. After microwave-assisted extraction, clean-up of samples was optimized using gel permeation chromatography and either stacked carbon and alumina solid-phase extraction cartridges or a deactivated Florisil column. Analytes were determined by gas chromatography with ion-trap mass spectrometry and electron capture detection. Method detection limits ranged from 0.6 to 8.9 ??g/kg dry weight. Bed and suspended sediments from a variety of locations were analyzed to validate the method and 29 pesticides, including at least 1 from every class, were detected.

  7. Comprehensive multi-residue method for the target analysis of pesticides in crops using liquid chromatography-tandem mass spectrometry.

    PubMed

    Hiemstra, Maurice; de Kok, André

    2007-06-22

    A liquid chromatography-tandem quadrupole mass spectrometry (LC-MS/MS) multi-residue method for the simultaneous target analysis of a wide range of pesticides and metabolites in fruit, vegetables and cereals has been developed. Gradient elution has been used in conjunction with positive mode electrospray ionization tandem mass spectrometry to detect up to 171 pesticides and/or metabolites in different crop matrices using a single chromatographic run. Pesticide residues were extracted/partitioned from the samples with acetone/dichloromethane/light petroleum. The analytical performance was demonstrated by the analysis of extracts from lettuce, orange, apple, cabbage, grape and wheat flour, spiked at three concentration levels ranging from 0.01 to 0.10 mg/kg for each pesticide and/or metabolite. In general, recoveries ranging from 70 to 110%, with relative standard deviations better than 15%, were obtained. The recovery and repeatability data are in good accordance with EU guidelines for pesticide residue analysis. The limit of quantification for all targeted pesticides and metabolites tested was 0.01 mg/kg. The selectivity and robustness of the LC-MS/MS method was demonstrated by a 1-year comparison of its analytical results with those obtained from our validated GC and LC multi-residue methods applied to more than 3500 routine samples. The validated LC-MS/MS method has been implemented in our analytical scheme since 2004, replacing four of the conventional detection methods, i.e. GC-flame-photometric detection (acephate, methamidophos, etc.), GC-nitrogen-phosphorus detection, LC-UV detection (carbendazim, thiabendazole, imazalil and prochloraz) and LC-fluorescence detection (N-methylcarbamate pesticides). During a 3-year period, the LC-MS/MS method has been applied to the analyses of more than 12,000 samples. PMID:17442324

  8. Multi-residue method for detecting coccidiostats at carry-over level in feed by HPLC-MS/MS.

    PubMed

    Delahaut, Ph; Pierret, G; Ralet, N; Dubois, M; Gillard, N

    2010-06-01

    A multi-residue HPLC-ESI-MS/MS method has been developed for the simultaneous extraction, detection and confirmation of the 11 coccidiostats referenced by Regulation 2009/8/EC (lasalocid sodium, narasin, salinomycin sodium, monensin sodium, semduramicin sodium, maduramicin ammonium alpha, robenidine hydrochloride, decoquinate, halofuginone hydrobromide, nicarbazin, and diclazuril) in feedstuffs at carry-over level. The sensitivity of the method allows quantification and confirmation for all coccidiostats below target concentration. The method was in-house validated and meets all criteria of European legislation (2002/657/EC). The precision of the method was determined under repeatability and within-laboratory reproducibility conditions; RSD(r) and RSD(R) were below the maximum permitted values for every tested concentration. The specificity was checked by analysing representative blank samples and blank samples fortified with potentially interfering substances (benzimidazoles, corticosteroides, triphenylmethane dyes, quinolones, nitrofurans, nitroimidazoles, phenicols); no interference were found. Concerning quantification, a quadratic regression model was fitted to every calibration curve with a regression coefficient r2 above 0.99 on each data set. Finally, the expanded uncertainty U was calculated with data obtained within the laboratory while applying the method during validation and in routine tests. PMID:20198524

  9. Multi-residue method for the determination of brominated and organophosphate flame retardants in indoor dust.

    PubMed

    Van den Eede, Nele; Dirtu, Alin C; Ali, Nadeem; Neels, Hugo; Covaci, Adrian

    2012-01-30

    A new method was optimized for the simultaneous determination of several flame retardants (FRs) in indoor dust, namely polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), novel brominated flame retardants (NBFRs) and organophosphate ester flame retardants (OPFRs). The method was based on two previously validated analytical methods for NBFRs and OPFRs, which were combined in order to include even a large number of FRs. An ultrasonic extraction method and two-stage clean-up by adsorption chromatography was optimized using an indoor dust standard reference material (SRM 2584). The 1st cleanup step was essential for fractionation of analytes in the dust extracts, while the 2nd step was important for the further removal of interferences. Analysis of cleaned dust extracts was performed with gas chromatography electron impact ionization mass spectrometry for OPFRs, gas chromatography electron capture negative ionization mass spectrometry for PBDEs and NBFRs and liquid chromatography electrospray ionization tandem mass spectrometry for HBCDs. Method validation by matrix spiking demonstrated good accuracy ranging from 81 to 130%. Matrix effects were investigated by spiking sodium sulfate and dust with analyte standards. Typical recoveries ranged between 80 and 110% at both spiking levels, though occasional deviations were observed at low spiking concentrations. Precision between different days was generally below 24% relative standard deviation (RSD) at low concentrations and below 11% RSD at high concentrations. Method limits of quantification for BFRs ranged between 0.04 (BDE 28) and 17 ng/g (BDE 209), 6 ng/g for sum HBCDs, and for OPFRs between 10 (triphenyl phosphate) and 370 ng/g (tri-isobutyl phosphate). The method was applied to SRM 2585 and to a set of indoor dust samples from various countries. The newly developed method will be employed for the monitoring of human exposure via dust ingestion to phased-out and alternate FRs. PMID:22284495

  10. Liquid chromatography-UV diode-array detection method for multi-residue determination of macrolide antibiotics in sheep's milk.

    PubMed

    García-Mayor, M A; Garcinuño, R M; Fernández-Hernando, P; Durand-Alegría, J S

    2006-07-28

    A rapid, simple and sensitive liquid chromatography-UV diode-array detection method was developed for the simultaneous determination of seven macrolides (erythromycin, oleandomycin, roxithromycin, josamycin, spiramycin, tylosin and ivermectin) in sheep's milk. The column, mobile phase, temperature and flow rate were optimised to provide the best resolution of these analytes. The extraction of the antibiotic residues involves the treatment of protein-free samples with a combination of concentrated sodium hydroxide and ethyl acetate. Necessary defatting is achieved by alkaline hydrolysis. The recovery of each antibiotic was between 55% and 77%, with relative standard deviations ranging from 1% to 6.5%. The limit of quantification was 72.4 microg/kg for ivermectin, 48.3 microg/kg for roxithromycin, and 24.1 microg/kg for erythromycin, oleandomycin, spiramycin, josamycin and tylosin. The procedure was successfully used in the multi-residue determination of these macrolides at levels below the maximum concentrations legally allowed in milk samples. PMID:16682049

  11. Multi-residue method for the analysis of pharmaceuticals and some of their metabolites in bivalves.

    PubMed

    Alvarez-Muñoz, D; Huerta, B; Fernandez-Tejedor, M; Rodríguez-Mozaz, S; Barceló, D

    2015-05-01

    A fast, simple and robust method has been developed for the simultaneous determination of 23 pharmaceuticals (including some major metabolites) in bivalve mollusks. The analytes belong to eight different therapeutic groups: antibiotics, psychiatric drugs, analgesics/anti-inflammatories, tranquilizer, calcium channel blockers, diuretic, and prostatic hyperplasia. The method is based on pressurized liquid extraction (PLE) followed by solid phase extraction clean-up (SPE), and ultra performance liquid chromatography-triple quadrupole mass spectrometry (UHPL-MS/MS) for the identification and quantification of the target analytes. It has been developed and validated in three different species of bivalves: Crassostrea gigas (Pacific oyster), Mytilus galloprovincialis (Mediterranean mussel), and Chamelea gallina (striped venus clam). The majority of the compounds were extracted with a recovery between 40 and 115%. The developed analytical method allowed the determination of the compounds in the lower ng/g concentration levels. The relative standard deviation was under 12% for the intra-day and 20% inter-day analyses, respectively. Finally, the method was applied to oyster, clam and mussel samples collected from the Ebro delta, Spain. The most ubiquitous compounds detected were the psychiatric drug venlanfaxine and the antibiotic azithromycin, with the highest concentrations found in mussel (2.7ng/g dw) and oyster (3.0ng/g dw), respectively. To the best of our knowledge, this is the first time that azithromycin has been reported in environmental samples of marine biota. PMID:25703000

  12. Rapid detection of pesticides not amenable to multi-residue methods by flow injection-tandem mass spectrometry.

    PubMed

    Mol, Hans G J; van Dam, Ruud C J

    2014-11-01

    Flow injection combined with tandem mass spectrometry (MS/MS) was investigated for the rapid detection of highly polar pesticides that are not amenable to multi-residue methods because they do not partition into organic solvents and require dedicated chromatographic conditions. The pesticides included in this study were amitrole, chlormequat, cyromazine, daminozide, diquat, ethephon, fosetyl-Al, glufosinate, glyphosate and its metabolite aminomethylphosphonic acid, maleic hydrazide, mepiquat and paraquat. The composition of the flow-injection solvent was optimized to achieve maximum MS/MS sensitivity. Instrumental limits of detection varied between <0.05 and 1 pg. Fruit, vegetable, cereal, milk and kidney samples were extracted with water (1% formic acid in case of paraquat/diquat) and ten times diluted in either methanol/0.1% formic acid, methanol/0.1% ammonia or acetonitrile/0.1% ammonia, depending on the pesticide. The ion suppression observed depended strongly on both the matrix and the pesticide. This could be largely compensated for by matrix-matched calibration, but more accurate quantification was obtained by using isotopically labelled standards (commercially available for most of the pesticides studied). The method detection limits ranged from 0.02 mg/kg for chlormequat and mepiquat to 2 mg/kg for maleic hydrazide and were 0.05-0.2 mg/kg for most other pesticide/matrix combinations. This was sufficiently low to test compliance with EU maximum residue limits for many relevant pesticide/commodity combinations. The method substantially reduces the liquid chromatography-MS/MS capacity demand which for many laboratories is prohibitive for inclusion of these pesticides in their monitoring and surveillance programmes. PMID:24518902

  13. A multi-residue method for characterization of endocrine disruptors in gaseous and particulate phases of ambient air

    NASA Astrophysics Data System (ADS)

    Alliot, Fabrice; Moreau-Guigon, Elodie; Bourges, Catherine; Desportes, Annie; Teil, Marie-Jeanne; Blanchard, Martine; Chevreuil, Marc

    2014-08-01

    A number of semi-volatile compounds occur in indoor air most of them being considered as potent endocrine disruptors and thus, exerting a possible impact upon health. To assess their concentration levels in indoor air, we developed and validated a method for sampling and multi-residue analysis of 58 compounds including phthalates, polycyclic aromatic hydrocarbons (PAHs), polybromodiphenylethers (PBDEs), polychlorobiphenyls (PCBs), parabens, bisphenol A (BPA) and tetrabromobisphenol A (TBBPA) in gaseous and particulate phases of air. We validated each step of procedures from extraction until analysis. Matrice spiking were performed at extraction, fractionation and purification stages. The more volatile compounds were analyzed with a gas chromatography system coupled with a mass spectrometer (GC/MS) or with a tandem mass spectrometer (GC/MS/MS). The less volatile compounds were analyzed with a liquid chromatography system coupled with a tandem mass spectrometer (LC/MS/MS). Labeled internal standard method was used ensuring high quantification accuracy. The instrumental detection limits were under 1 pg for all compounds and therefore, a limit of quantification averaging 1 pg m-3 for the gaseous and the particulate phases and a volume of 150 m3, except for phthalates, phenol compounds and BDE-209. Satisfactory recoveries were found except for phenol compounds. That method was successfully applied to several indoor air samples (office, apartment and day nursery) and most of the targeted compounds were quantified, mainly occurring in the gaseous phase. The most abundant were phthalates (up to 918 ng m-3 in total air), followed by PCBs > parabens > BPA > PAHs > PBDEs.

  14. Modification and re-validation of the ethyl acetate-based multi-residue method for pesticides in produce

    PubMed Central

    Rooseboom, Astrid; van Dam, Ruud; Roding, Marleen; Arondeus, Karin; Sunarto, Suryati

    2007-01-01

    The ethyl acetate-based multi-residue method for determination of pesticide residues in produce has been modified for gas chromatographic (GC) analysis by implementation of dispersive solid-phase extraction (using primary–secondary amine and graphitized carbon black) and large-volume (20 μL) injection. The same extract, before clean-up and after a change of solvent, was also analyzed by liquid chromatography with tandem mass spectrometry (LC–MS–MS). All aspects related to sample preparation were re-assessed with regard to ease and speed of the analysis. The principle of the extraction procedure (solvent, salt) was not changed, to avoid the possibility invalidating data acquired over past decades. The modifications were made with techniques currently commonly applied in routine laboratories, GC–MS and LC–MS–MS, in mind. The modified method enables processing (from homogenization until final extracts for both GC and LC) of 30 samples per eight hours per person. Limits of quantification (LOQs) of 0.01 mg kg−1 were achieved with both GC–MS (full-scan acquisition, 10 mg matrix equivalent injected) and LC–MS–MS (2 mg injected) for most of the pesticides. Validation data for 341 pesticides and degradation products are presented. A compilation of analytical quality-control data for pesticides routinely analyzed by GC–MS (135 compounds) and LC–MS–MS (136 compounds) in over 100 different matrices, obtained over a period of 15 months, are also presented and discussed. At the 0.05 mg kg−1 level acceptable recoveries were obtained for 93% (GC–MS) and 92% (LC–MS–MS) of pesticide–matrix combinations. PMID:17563885

  15. A multi-residue method for the determination of seven polypeptide drug residues in chicken muscle tissues by LC-MS/MS.

    PubMed

    Boison, Joe O; Lee, Stephen; Matus, Johanna

    2015-05-01

    A new multi-residue method for the determination of seven polypeptides, namely, polymixin B1, polymixin B2, polymixin E1 (colistin A), polymixin E2 (colistin B), enduracidin A (enramycin A), enduracidin B (enramycin B), and bacitracin A, in food of animal origin was developed and validated for chicken muscle tissue. Chicken muscle tissue was extracted with acidified methanol (1 % TFA). After homogenization, shaking, and centrifugation, the acidified methanol extract was decanted. A second extraction was performed with methanol (1 % TFA) and formic acid (1 %) 25:75, v/v. The pooled extract was cleaned up and concentrated on a solid-phase extraction cartridge. The retained analytes were eluted with methanol/acetonitrile. The extract was evaporated to dryness, reconstituted in mobile phase, filtered, and quantified by LC-MS/MS under ESI conditions. The method has a LOQ of 50.0 μg/kg for polymixin E2 (colistin B), 39.0 μg/kg for polymixin E1 (colistin A), 74.0 μg/kg for polymixin B1, 71.0 μg/kg for polymixin B2, 66.0 μg/kg for enduracidin A, 50.0 μg/kg for enduracidin B, and 30.0 μg/kg for bacitracin A in chicken muscle tissues. This is the first sensitive, suitable, multi-residue method reported for the seven polypeptide drug residues in chicken muscle tissue. PMID:25832483

  16. A sensitive multi-residue method for the determination of 35 micropollutants including pharmaceuticals, iodinated contrast media and pesticides in water.

    PubMed

    Valls-Cantenys, Carme; Scheurer, Marco; Iglesias, Mònica; Sacher, Frank; Brauch, Heinz-Jürgen; Salvadó, Victoria

    2016-09-01

    A sensitive, multi-residue method using solid-phase extraction followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed to determine a representative group of 35 analytes, including corrosion inhibitors, pesticides and pharmaceuticals such as analgesic and anti-inflammatory drugs, five iodinated contrast media, β-blockers and some of their metabolites and transformation products in water samples. Few other methods are capable of determining such a broad range of contrast media together with other analytes. We studied the parameters affecting the extraction of the target analytes, including sorbent selection and extraction conditions, their chromatographic separation (mobile phase composition and column) and detection conditions using two ionisation sources: electrospray ionisation (ESI) and atmospheric pressure chemical ionisation (APCI). In order to correct matrix effects, a total of 20 surrogate/internal standards were used. ESI was found to have better sensitivity than APCI. Recoveries ranging from 79 to 134 % for tap water and 66 to 144 % for surface water were obtained. Intra-day precision, calculated as relative standard deviation, was below 34 % for tap water and below 21 % for surface water, groundwater and effluent wastewater. Method quantification limits (MQL) were in the low ng L(-1) range, except for the contrast agents iomeprol, amidotrizoic acid and iohexol (22, 25.5 and 17.9 ng L(-1), respectively). Finally, the method was applied to the analysis of 56 real water samples as part of the validation procedure. All of the compounds were detected in at least some of the water samples analysed. Graphical Abstract Multi-residue method for the determination of micropollutants including pharmaceuticals, iodinated contrast media and pesticides in waters by LC-MS/MS. PMID:27382969

  17. Chemometric approach to open validation protocols: Prediction of validation parameters in multi-residue ultra-high performance liquid chromatography-tandem mass spectrometry methods.

    PubMed

    Alladio, Eugenio; Pirro, Valentina; Salomone, Alberto; Vincenti, Marco; Leardi, Riccardo

    2015-06-01

    The recent technological advancements of liquid chromatography-tandem mass spectrometry allow the simultaneous determination of tens, or even hundreds, of target analytes. In such cases, the traditional approach to quantitative method validation presents three major drawbacks: (i) it is extremely laborious, repetitive and rigid; (ii) it does not allow to introduce new target analytes without starting the validation from its very beginning and (iii) it is performed on spiked blank matrices, whose very nature is significantly modified by the addition of a large number of spiking substances, especially at high concentration. In the present study, several predictive chemometric models were developed from closed sets of analytes in order to estimate validation parameters on molecules of the same class, but not included in the original training set. Retention time, matrix effect, recovery, detection and quantification limits were predicted with partial least squares regression method. In particular, iterative stepwise elimination, iterative predictors weighting and genetic algorithms approaches were utilized and compared to achieve effective variables selection. These procedures were applied to data reported in our previously validated ultra-high performance liquid chromatography-tandem mass spectrometry multi-residue method for the determination of pharmaceutical and illicit drugs in oral fluid samples in accordance with national and international guidelines. Then, the partial least squares model was successfully tested on naloxone and lormetazepam, in order to introduce these new compounds in the oral fluid validated method, which adopts reverse-phase chromatography. Retention time, matrix effect, recovery, limit of detection and limit of quantification parameters for naloxone and lormetazepam were predicted by the model and then positively compared with their corresponding experimental values. The whole study represents a proof-of-concept of chemometrics potential to

  18. Validation of a multi-residue method to determine deltamethrin and alpha-cypermethrin in mosquito nets by gas chromatography with electron capture detection (GC-μECD)

    PubMed Central

    2013-01-01

    Background Nowadays long-lasting insecticidal mosquito nets (LNs) are frequently used around the world to protect people against malaria vectors. As they contain insecticide, laboratory control is needed to check whether the content of the active ingredient follows the conditions of the manufacturer and also if the active ingredient is still present after some time of use. For this purpose, an analytical method had to be developed. The fact that LNs include a range of polymers for the yarn and use coated or incorporated technologies for the active ingredient, it is a challenge to find only one analytical method determining the active ingredient in LNs, which takes into account both impregnation technologies. Some methods are provided by international organizations but are limited by the determination of only one pesticide per method. The aim of this study was to optimize a short time extraction method for deltamethrin and alpha-cypermethrin from coated and incorporated mosquito nets and also to detect both insecticides in one analytical run, using gas chromatography with electron capture detection (GC-μECD). Methods Based on the literature, the most suitable solvent and the adequate extraction process for the insecticides used for net making were identified and adapted for the new multi-residue method. Results The validation data of the multi-residue method to determine deltamethrin and alpha-cypermethrin in mosquito nets by GC-μECD are given. Depending on the concentration of the active ingredient spiked on the nets, the mean recovery for alpha-cypermethrin ranged between 86% and 107% with a relative standard deviation below 3.5%. For deltamethrin it ranged between 90% and 108% with a relative standard deviation also below 3.5%. The limit of detection is 0.009 g.a.i/kg of net (0.3 mg a.i./m2 of net) both for alpha-cypermethrin and deltamethrin. Conclusions Data obtained are excellent. A 30 minutes reflux extraction method with xylene was developed to determine

  19. Optimisation and validation of a quantitative and confirmatory LC-MS method for multi-residue analyses of β-lactam and tetracycline antibiotics in bovine muscle.

    PubMed

    Rezende, C P; Almeida, M P; Brito, R B; Nonaka, C K; Leite, M O

    2012-01-01

    A multi-residue method for the determination of the β-lactam antibiotics ampicillin, cefazolin, cloxacillin, dicloxacillin, nafcillin, oxacillin, penicillin G, penicillin V and the tetracyclines chlotetracycline, tetracycline and oxytetracycline was optimised and validated in bovine muscle. The method is based on the extraction of the residues from muscle using water/acetonitrile (2/8, v/v) with subsequent use of dispersive solid-phase C18 and hexane for purification. Extracts were analysed using ultra-performance liquid chromatography (UPLC-MS/MS) coupled with the mass spectrometer in positive electrospray ionisation mode (ESI+) for all analytes. The method was validated according to the requirements of European Commission Decision 2002/657/EC. The validation results were obtained within the MRL range of 0-1.5 of the MRL, with recoveries varying from 90% to 110% and CV < 20% (n = 54), except for cloxacillin, dicloxacillin and nafcillin. However, matrix interference was observed. The decision limit (CCα) ranged from 10% to 15% of the MRL. The uncertainty measurement was estimated based on both bottom-up and top-down strategies and the uncertainty values were found to be lower than 20% of the MRL. The method has a simple extraction procedure whereby analytes are separated with reasonable resolutions in a single 11-min chromatographic run. According to the validation results, this method is suitable for monitoring β-lactams and tetracyclines according to National Program for Residue and Contaminant Control - Brazil (NPRC-Brazil) in bovine muscle. PMID:22070766

  20. Validation and application of a multi-residue method, using accelerated solvent extraction followed by gas chromatography, for pesticides quantification in soil.

    PubMed

    Leyva-Morales, J B; Valdez-Torres, J B; Bastidas-Bastidas, P J; Betancourt-Lozano, M

    2015-01-01

    A multi-residue method was developed to determine different types of pesticides in soils. An extraction with pressure and temperature, through accelerated solvent extraction (dichloromethane:acetone, 50:50, v/v). The pesticides were determined by gas chromatography with several selective detectors: electron capture detector, pulsed flame photometric detector and thermionic specific detector. The following parameters were determined: limit of detection, limit of quantification, equipment linearity (working interval), method linearity as well as, method accuracy and precision. The average recoveries ranged between 76 and 106%, with the exception of chlorothalonil, which had an average recovery of 46%. Additionally, detection limits from 0.9 to 7.6ng g -: (1) and the quantification limits from 3.00 to 25.47ng g -: (1) were estimated. In terms of linearity and precision, the results obtained were in the ranges considered adequate (R(2) ≥ 0.98 and coefficient of variation (CV) ≤ 20%), with the exception of aldrin (R(2) = 0.946, CV = 35.79%), lindane (R(2) = 0.917, CV = 32.91%) and chlorothalonil (R(2) = 0.8184, CV = 81.35%). The proposed method was used to evaluate pesticides in real soil samples, detecting concentrations over 1000ng g -: (1) for some pesticides. The method was correctly validated and provided for the rapid determination of pesticides in soil. PMID:26041247

  1. A multi-residue method for determination of 70 organic micropollutants in surface waters by solid-phase extraction followed by gas chromatography coupled to tandem mass spectrometry.

    PubMed

    Terzopoulou, Evangelia; Voutsa, Dimitra; Kaklamanos, George

    2015-01-01

    A multi-residue method, based on gas chromatography coupled to tandem mass spectrometry (GC-MS/MS), has been developed for the determination of 70 organic micropollutants from various chemical classes (organochlorinated, organophosphorous, triazines, carbamate and urea, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, pharmaceuticals, phenols, etc.) in surface waters. A single-step SPE extraction using OASIS HLB cartridges was employed for the recovery of target micropollutants. The method has been validated according to monitoring performance criteria of the Water Framework Directive, taking into account the approved guidelines on quality assurance and quality control. The recoveries ranged from 60 to 110 %, the coefficient of variation from 0.84 to 27.4 %, and the uncertainty from 6 to 37 %. The LOD varied from 6.0 to 40 ng/L. The limits of quantification for the priority pollutants anthracene, alachlor, atrazine, benzo(a)pyrene, chlorfenvinphos, diuron, isoproturon, nonylphenol, simazine, and terbutryn fulfill the criterion of <30 % of the relevant environmental standards. The method was employed to investigate the water quality in the basin of a transboundary river, Strymonas, in NE Greece during three sampling campaigns conducted in the year 2013. Thirty-nine compounds were detected in the river water. Metolachlor, diuron, isoproturon, salicylic acid, chlorfenvinphos, 1,2-benzanthracene, pyrene, diflubenzuron, and carbaryl exhibited the highest detection frequencies. PMID:25109470

  2. A multi-residue method for 17 anticoccidial drugs and ractopamine in animal tissues by liquid chromatography-tandem mass spectrometry and time-of-flight mass spectrometry.

    PubMed

    Matus, Johanna L; Boison, Joe O

    2016-05-01

    A new and sensitive multi-residue liquid chromatography-tandem mass spectrometry (LC-MS/MS) and liquid chromatography-quadrupole time-of-flight-mass spectrometry (LC-QToF-MS) method was developed and validated for the determination and confirmation of residues of 17 anticoccidials, plus free ractopamine in poultry muscle and liver, and bovine muscle, liver, and kidney tissues. The 17 anticoccidials are lasalocid, halofuginone, narasin, monensin, semduramicin, ethopabate, robenidine, buquinolate, toltrazuril as its sulfone metabolite, maduramicin, salinomycin, diclazuril, amprolium, decoquinate, dinitolmide, clopidol, and the nicarbazin metabolite DNC (N,N1-bis(4-nitrophenyl)urea). The analytes were extracted and cleaned up within a 3-hour period by simply extracting the analytes into a solvent mixture with salts followed by centrifugation, dilution, and filtration. The validated method was used in a pilot study for the analysis of 173 samples that included quail liver, bovine kidney, liver, muscle, and horse muscle. The predominant residues found in this study were monensin, ractopamine, and lasalocid. The results of this pilot study showed that this new method is applicable to real samples, and is fit for use in a regulatory testing programme. © 2016 Her Majesty the Queen in Right of Canada. Drug Testing and Analysis. © 2016 John Wiley & Sons, Ltd. PMID:27443201

  3. [Study of multi-residue method for determining pesticide residues in processed foods manufactured from agricultural products by LC-MS/MS].

    PubMed

    Fukui, Naoki; Takatori, Satoshi; Kitagawa, Yoko; Okihashi, Masahiro; Kajimura, Keiji; Obana, Hirotaka

    2013-01-01

    A rapid multi-residue method for determination of pesticide residues in processed foods manufactured from agricultural products was examined. Five mL water was added to 5 g sample in a polypropylene tube, and the tube was left to stand at room temperature for 30 min. Then, 20 mL acetonitrile was added to the sample. The mixture was homogenized in a high-speed homogenizer, followed by salting out with 1 g NaCl and 4 g anhydrous MgSO4. After centrifugation, the organic layer was purified on a graphitized carbon/PSA cartridge column. After removal of the solvent, the extract was resolved in methanol-water and analyzed with LC-MS/MS. The recoveries of 93 pesticides fortified into 5 kinds of processed foods [Chinese cabbage kimchi, marmalade, raisin, umeboshi (pickled plum) and worcester sauce] were examined at the concentrations of 0.02 and 0.1 μg/g (n=5). The recoveries of 61 pesticides in all foods were 70-120% with relative standard deviation below 20% at both concentrations. Seventy-four processed foods obtained from markets in Japan were examined with this method. Pesticide residues over the maximum residue limit (0.01 μg/g) were detected in 2 processed foods. PMID:24389475

  4. Multi-residue confirmatory method for the determination of twelve coccidiostats in chicken liver using liquid chromatography tandem mass spectrometry.

    PubMed

    Olejnik, Małgorzata; Szprengier-Juszkiewicz, Teresa; Jedziniak, Piotr

    2009-11-13

    The confirmatory LC-MS/MS method for the determination of residues for twelve coccidiostats including ionophore antibiotics (lasalocid, maduramycin, monensin, narasin, salinomycin, semduramycin) and chemical coccidiostats (clazuril, decoquinate, diclazuril, halofuginone, nicarbazin and robenidine) in poultry liver has been developed. The sample preparation was based on extraction with acetonitrile, defatting with Alumina columns and clean-up on Oasis HLB spe. The separation of analytes was performed on PhenylHexyl column with a gradient of acetonitrile, methanol and the ammonium formate pH 4.0. For all analytes, at least 2 diagnostic fragmentation ions were monitored. The validation, performed according to the CD 2002/657/EC, proved the suitability of the method for the confirmatory analysis of the coccidiostats. For lasalocid, however, low reproducibility was observed and the proper quantification could not be performed with this method. PMID:19481216

  5. Simplified RP-HPLC method for multi-residue analysis of abamectin, emamectin benzoate and ivermectin in rice.

    PubMed

    Xie, Xianchuan; Gong, Shu; Wang, Xiaorong; Wu, Yinxing; Zhao, Li

    2011-01-01

    A rapid, reliable and sensitive reverse-phase high-performance liquid chromatography method with fluorescence detection (RP-FLD-HPLC) was developed and validated for simultaneous analysis of the abamectin (ABA), emamectin (EMA) benzoate and ivermectin (IVM) residues in rice. After extraction with acetonitrile/water (2 : 1) with sonication, the avermectin (AVMs) residues were directly derivatised by N-methylimidazole (N-NMIM) and trifluoroacetic anhydride (TFAA) and then analysed on RP-FLD-HPLC. A good linear relationship (r(2 )> 0.99) was obtained for three AVMs ranging from 0.01 to 5 microg ml(-1), i.e. 0.01-5.0 microg g(-1) in rice matrix. The limit of detection (LOD) and the limit of quantification (LOQ) were between 0.001 and 0.002 microg g(-1) and between 0.004 and 0.006 microg g(-1), respectively. Recoveries were from 81.9% to 105.4% and precision less than 12.4%. The proposed method was successfully applied to routine analysis of the AVMs residues in rice. PMID:21132591

  6. Development of a sulfonamide ELISA and its comparison with LC-MS/MS method

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sulfonamides are common chemotherapeutic agents used in veterinary and human medicines to treat bacterial and protozoa infections. Because of their widespread usage sulfonamides, such as sulfamethoxazole, are some of the most prevalent pharmaceuticals found in waterways. A sulfonamide ELISA has be...

  7. Multi-walled carbon nanotubes as alternative reversed-dispersive solid phase extraction materials in pesticide multi-residue analysis with QuEChERS method.

    PubMed

    Zhao, Pengyue; Wang, Lei; Zhou, Li; Zhang, Fengzu; Kang, Shu; Pan, Canping

    2012-02-17

    A multi-residue method based on modified QuEChERS sample preparation with multi-walled carbon nanotubes (MWCNTs) as reversed-dispersive solid phase extraction (r-DSPE) material and gas chromatography-mass spectrometry determination by selected ion monitoring (GC/MS-SIM) mode was validated on 30 representative pesticides residues in vegetables and fruits. The acetonitrile-based QuEChERS (quick, easy, cheap, effective, rugged and safe) sample preparation technique was used to obtain the extracts, and the further cleanup was carried out by applying r-DSPE. It was found that the amount of MWCNTs influenced the cleanup performance and the recoveries. The optimal amount of 10mg MWCNTs was suitable for cleaning up all selected matrices, as a suitable alternative r-DSPE material to primary secondary amine (PSA). This method was validated on cabbage, spinach, grape and orange spiked at concentration levels of 0.02 and 0.2 mg/kg. The recoveries of 30 pesticides were in the range of 71-110%, with relative standard deviations (RSDs, n=5) lower than 15%. Matrix effects were observed by comparing the slope of matrix-matched standard calibration with that of solvent. Good linearity was achieved at the concentration levels of 0.02-0.5 mg/L. The limits of quantification (LOQs) and the limits of detection (LODs) for 30 pesticides ranged from 0.003 to 0.05 mg/kg and 0.001 to 0.02 mg/kg at the signal-to-noise ratio (S/N) of 10 and 3, respectively. The method was successfully applied to analysis real samples in Beijing. In conclusion, the modified QuEChERS method with MWCNTs cleanup step showed reliable method validation performances and good cleanup effects in this study. PMID:22227363

  8. Multi-residue method for the determination of 57 persistent organic pollutants in human milk and colostrum using a QuEChERS-based extraction procedure.

    PubMed

    Luzardo, Octavio P; Ruiz-Suárez, Norberto; Almeida-González, Maira; Henríquez-Hernández, Luis Alberto; Zumbado, Manuel; Boada, Luis D

    2013-11-01

    Human breast milk represents the best choice for the nutrition of infants. However, in addition to containing beneficial nutrients and antibodies, it can also be considered the best indicator of infant exposure to contaminants. We developed a multi-residue method using a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure and capillary gas chromatography-triple quadrupole mass spectrometry for the determination of 57 persistent organic pollutants, including 23 organochlorine pesticides, 18 polychlorinated biphenyl (PCB) congeners, and 16 polycyclic aromatic hydrocarbons in human milk and colostrum samples. We have used primary secondary amine in the clean-up step as it gave a more efficient separation of the analytes from fat and superior removal of the co-extracted substances compared with gel permeation chromatography. No significant matrix effect was observed for the tested pollutants, and therefore matrix-matched calibration was not necessary. The average recoveries from spiked samples were in the range of 74.8-113.0 %. The precision was satisfactory, with relative standard deviations below 16 %, while values of 0.1-0.4 μg L(-1) were established as the limit of quantification for all the target analytes (0.05 and 100 μg L(-1)). The method was successfully applied to the analysis of 18 human colostrum and 23 mature milk samples. All the samples tested were positive for at least nine different residues, with some samples containing up to 24 contaminants. Remarkably, the contaminants hexachlorobenzene, p,p'-DDE, PCB 138, PCB 180, phenanthrene, fluoranthene, and pyrene were present in 100 % of the colostrum and mature milk samples analyzed. PMID:24162817

  9. Multi-residue method for trace level determination of pharmaceuticals in environmental samples using liquid chromatography coupled to triple quadrupole mass spectrometry.

    PubMed

    Grabic, Roman; Fick, Jerker; Lindberg, Richard H; Fedorova, Ganna; Tysklind, Mats

    2012-10-15

    A multi-residue method for the simultaneous determination of more than 90 pharmaceuticals in water samples was developed and validated. The developed method utilizes a single liquid chromatography-tandem mass spectrometry (LC-MS/MS) run after sample enrichment using solid-phase extraction (SPE). The pharmaceuticals included in this method were chosen based on their potency (effect/concentration ratio) and potential to bioaccumulate in fish. Because the selection was based on ecotoxicological criteria and not on ease of detection, the pharmaceuticals have a wide range of physico-chemical properties and represent 27 distinct classes. No method for surface, waste water or similar matrices was previously described for 52 of the 100 target analytes. Four chromatographic columns were tested to optimize the separation prior to detection by mass spectrometry (MS). The resulting method utilizes a Hypersil Gold aQ column. Three different water matrices were tested during method validation: Milli-Q water, surface water (river water from the Umea River) and effluent from the Umea waste water treatment plant (WWTP). Four of the selected pharmaceuticals exhibited poor method efficiency in all matrices. Amiodarone, Dihydroergotamine, Perphenazine and Terbutalin were omitted from the final analytical method. In addition, five compounds were excluded from the method for surface water (Atorvastatin, Chloropromazin, Dipyridamol, Furosemid and Ranitidin) and three other pharmaceuticals (Glibenclamid, Glimepirid and Meclozine) from waste water method respectively. Absolute recoveries were above 70% for Milli-Q water, surface water, and sewage effluent for most pharmaceuticals. The limits of quantification (LOQs) ranged from 0.05 to 50 ng L(-1) (median 5 ng L(-1)). The use of matrix-matched standards led to the elimination of ionization enhancement or suppression. The recoveries of the method for real matrices were in the range of 23-134% for surface water (only three compounds were

  10. Development of an immunoaffinity column method using broad-specificity monoclonal antibodies for simultaneous extraction and cleanup of quinolone and sulfonamide antibiotics in animal muscle tissues

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This paper describes a novel mixed-bed immunoaffinity column (IAC) method. The IAC was produced by coupling anti-fluoroquinolone and anti-sulfonamide broad-specificity monoclonal antibodies (Mabs) to Sepharose 4B for simultaneously isolating 13 fluoroquinolones (FQs) and 6 sulfonamides (SAs) from s...

  11. Development of an immunoaffinity chromatography and HPLC-UV method for determination of 16 sulfonamides in feed.

    PubMed

    Kim, Ho Jin; Jeong, Min Hee; Park, Hye Jin; Kim, Won Chan; Kim, Jang Eok

    2016-04-01

    A novel and simple method for detecting 16 sulfonamides (SAs) in animal feed using high performance liquid chromatography equipped with a photo-diode array detector (HPLC/PDA) and immunoaffinity chromatography was developed. The chromatographic peaks of the 16 SAs were successfully identified by comparing their retention times and UV spectra with reference standards. Method validation was performed with linearity, sensitivity, selectivity, accuracy and precision. The limits of detection (LODs) for the instrument used to study sulfonamides ranged from 14.1 to 45.0 μg/kg, and the limits of quantification (LOQs) ranged from 46.9 to 150.0 μg/kg. Average recoveries of the 16 SAs ranged from 78.2% to 105.2%. Method replication resulted in intraday and interday peak area variation of <5.5%. The developed method was specific and reliable and is suited for the routine analysis of SAs in animal feed. PMID:26593600

  12. A simple, accurate, time-saving and green method for the determination of 15 sulfonamides and metabolites in serum samples by ultra-high performance supercritical fluid chromatography.

    PubMed

    Zhang, Yuan; Zhou, Wei-E; Li, Shao-Hui; Ren, Zhi-Qin; Li, Wei-Qing; Zhou, Yu; Feng, Xue-Song; Wu, Wen-Jie; Zhang, Feng

    2016-02-01

    An analytical method based on ultra-high performance supercritical fluid chromatography (UHPSFC) with photo-diode array detection (PDA) has been developed to quantify 15 sulfonamides and their N4-acetylation metabolites in serum. Under the optimized gradient elution conditions, it took only 7min to separate all 15 sulfonamides and the critical pairs of each parent drug and metabolite were completely separated. Variables affecting the UHPSFC were optimized to get a better separation. The performance of the developed method was evaluated. The UHPSFC method allowed the baseline separation and determination of 15 sulfonamides and metabolites with limit of detection ranging from 0.15 to 0.35μg/mL. Recoveries between 90.1 and 102.2% were obtained with satisfactory precision since relative standard deviations were always below 3%. The proposed method is simple, accurate, time-saving and green, it is applicable to a variety of sulfonamides detection in serum samples. PMID:26780846

  13. Multiresidue supercritical fluid extraction method for the recovery at low ppb levels of three sulfonamides from fortified chicken liver.

    PubMed

    Maxwell, R J; Lightfield, A R

    1998-09-18

    A supercritical fluid extraction (SFE) method is proposed for the recovery of three sulfonamides from chicken liver. Samples were extracted at 680 bar and 40 degrees C using unmodified carbon dioxide and were collected free of co-extracted artifactual material on an in-line neutral alumina sorbent bed. High recoveries of sulfamethazine (SMZ), sulfadimethoxine (SDM) and sulfaquinoxaline (SQX) were obtained from chicken liver samples fortified at levels from 1000 to 50 ppm. PMID:9792530

  14. Agar disk elution method for susceptibility testing of Mycobacterium marinum and Mycobacterium fortuitum complex to sulfonamides and antibiotics.

    PubMed Central

    Stone, M S; Wallace, R J; Swenson, J M; Thornsberry, C; Christensen, L A

    1983-01-01

    An agar disk elution method using round well plates, supplemented Mueller-Hinton agar, and commercial drug disks is described for susceptibility testing of Mycobacterium marinum and the rapidly growing mycobacteria to antibiotics and sulfonamides. By this method, 14 of 14 strains of M. marinum were susceptible to rifampin, doxycycline, minocycline, and trimethoprim-sulfamethoxazole. Identical results were obtained with Middlebrook 7H10 agar and drugs prepared from standard powders. With 58 isolates of Mycobacterium fortuitum and Mycobacterium chelonei, this method had a 92% correlation with broth minimal inhibitory concentration determinations for cefoxitin and greater than 98% for doxycycline, kanamycin, amikacin, and the sulfonamides. Sixty-nine percent of isolates of M. chelonei susceptible to amikacin on supplemented Mueller-Hinton agar were resistant on 7H10 agar, and 15 of 16 M. chelonei isolates susceptible to erythromycin in broth were resistant by disk elution when an endpoint of no growth was used with either agar. The agar disk elution method offers a practical method for testing of most antibacterial agents against these mycobacterial species. Images PMID:6651277

  15. Comparison of an acetonitrile extraction/partitioning and "dispersive solid-phase extraction" method with classical multi-residue methods for the extraction of herbicide residues in barley samples.

    PubMed

    Díez, C; Traag, W A; Zommer, P; Marinero, P; Atienza, J

    2006-10-27

    An acetonitrile/partitioning extraction and "dispersive solid-phase extraction (SPE)" method that provides high quality results with a minimum number of steps and a low solvent and glassware consumption was published in 2003. This method, suitable for the analysis of multiple classes of pesticide residues in foods, has been given an acronymic name, QuEChERS, that reflects its major advantages (quick, easy, cheap, effective, rugged, safe). In this work, QuEChERS method, which was originally created for vegetable samples with a high amount of water, was modified to optimise the extraction of a wide range of herbicides in barley. Then, it was compared with known conventional multi-residue extraction procedures such as the Luke method, which was simplified and shortened by eliminating the Florisil clean-up (mini Luke) and the ethyl acetate extraction, which involves a subsequent clean-up by gel permeation chromatography (GPC) and which is the official extraction method used by some of European authorities. Finally, a simple acetone extraction was carried out to check the differences with the other three methods. Extracts were analysed by gas chromatography-time-of-flight mass spectrometry (GC-TOF/MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). Mini Luke was significantly more effective for the extraction of non-polar and medium-polar compounds, but the best recoveries for polar compounds were achieved by QuEChERS and ethyl acetate methods. QuEChERS was the only method that provided an overall recovery value of 60-70% for non-, medium- and polar compounds, with some exceptions due to co-eluted matrix interferences. Clean-up by dispersive SPE was effective and did not differ so much with ethyl acetate extracts considering that QuEChERS clean-up step is much easier and less time-consuming. As a conclusion, it resulted to be the most universal extraction method by providing a well-defined phase separation without dilution and achieving acceptable

  16. Development and validation of an LC-UV method for the determination of sulfonamides in animal feeds.

    PubMed

    Kumar, P; Companyó, R

    2012-05-01

    A simple LC-UV method was developed for the determination of residues of eight sulfonamides (sulfachloropyridazine, sulfadiazine, sulfadimidine, sulfadoxine, sulfamethoxypyridazine, sulfaquinoxaline, sulfamethoxazole, and sulfadimethoxine) in six types of animal feed. C18, Oasis HLB, Plexa and Plexa PCX stationary phases were assessed for the clean-up step and the latter was chosen as it showed greater efficiency in the clean-up of interferences. Feed samples spiked with sulfonamides at 2 mg/kg were used to assess the trueness (recovery %) and precision of the method. Mean recovery values ranged from 47% to 66%, intra-day precision (RSD %) from 4% to 15% and inter-day precision (RSD %) from 7% to 18% in pig feed. Recoveries and intra-day precisions were also evaluated in rabbit, hen, cow, chicken and piglet feed matrices. Calibration curves with standards prepared in mobile phase and matrix-matched calibration curves were compared and the matrix effects were ascertained. The limits of detection and quantification in the feeds ranged from 74 to 265 µg/kg and from 265 to 868 µg/kg, respectively. PMID:21671426

  17. 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

    2016-09-01

    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. PMID:27499107

  18. A simple and efficient multi-residue method based on QuEChERS for pesticides determination in palm oil by liquid chromatography time-of-flight mass spectrometry.

    PubMed

    Sobhanzadeh, Elham; Abu Bakar, Nor Kartini; Bin Abas, Mhd Radzi; Nemati, Keivan

    2012-09-01

    In this study, a rapid, specific and sensitive multi-residue method based on acetonitrile extraction followed by dispersive solid-phase extraction (d-SPE) clean-up was implemented and validated for multi-class pesticide residues determination in palm oil for the first time. Liquid-liquid extraction followed by low-temperature precipitation procedure was evaluated in order to study the freezing-out clean-up efficiency to obtain high recovery yield and low co-extract fat residue in the final extract. For clean-up step, d-SPE was carried out using a combination of anhydrous magnesium sulphate (MgSO(4)), primary secondary amine, octadecyl (C(18)) and graphitized carbon black. Recovery study was performed at two concentration levels (10 and 100 ng g(-1)), yielding recovery rates between 74.52% and 97.1% with relative standard deviation values below 10% (n = 6) except diuron. Detection and quantification limits were lower than 5 and 9 ng g(-1), respectively. In addition, soft matrix effects (≤±20%) were observed for most of the studied pesticides except malathion that indicated medium (20-50%) matrix effects. The proposed method was successfully applied to the analysis of suspected palm oil samples. PMID:21989900

  19. Scope extension validation protocol: inclusion of analytes and matrices in an LC-MS/MS sulfonamide residues method.

    PubMed

    Hoff, Rodrigo Barcellos; Barreto, Fabiano; Melo, Jéssica; Martins, Magda Targa; Pizzolato, Tânia Mara; Peralba, Maria do Carmo Ruaro

    2014-01-01

    Validation is a required process for analytical methods. However, scope extension, i.e. inclusion of more analytes, other matrices and/or minor changes in extraction procedures, can be achieved without a full validation protocol, which requires time and is laborious to the laboratory. This paper presents a simple and rugged protocol for validation in the case of extension of scope. Based on a previously reported method for analysis of sulfonamide residues using LC-MS/MS, inclusion of more analytes, metabolites, matrices and optimisation for the extraction procedure are presented in detail. Initially, the method was applied only to liver samples. In this work, milk, eggs and feed were also added to the scope. Several case-specific validation protocols are proposed for extension of scope. PMID:24195474

  20. Multi-residue method for the determination of organofluorine pesticides in fish tissue by liquid chromatography triple quadrupole tandem mass spectrometry.

    PubMed

    Gan, Jinhua; Lv, Lei; Peng, Jie; Li, Jinping; Xiong, Zhiting; Chen, Daqing; He, Li

    2016-09-15

    A multiresidue method for the determination of organofluorine pesticides in fish tissue samples was developed and optimized. This method is based on a cleanup step of the extracted samples with acetonitrile, and carried out by solid phase extraction (SPE) with aminopropyl (NH2) cartridge, before the identification and quantification of the residues by liquid chromatography triple quadrupole tandem mass spectrometry (LC-MS/MS). The performance characteristics, such as accuracy, precision, linear range, limits of detection (LOD) and quantification (LOQ), for each pesticide were determined. The proposed method allowed high recoveries (80.4-99.2%) of spiked extracted fat samples at 0.5-10 ng g(-1), and very low LODs (between 0.10 and 0.15 ng g(-1)) and LOQs (between 0.3 and 0.5 ng g(-1)) determined in the fish samples. The practicality and high sensitivity of this method have been demonstrated in the determination of residues of OFPs in carp fish fed in water containing 10 ng mL(-1) OFPs. PMID:27080897

  1. Development of high-throughput multi-residue method for non-steroidal anti-inflammatory drugs monitoring in swine muscle by LC-MS/MS.

    PubMed

    Castilhos, Tamara S; Barreto, Fabiano; Meneghini, Leonardo; Bergold, Ana Maria

    2016-07-01

    A reliable and simple method for the detection and quantification of residues of 14 non-steroidal anti-inflammatory drugs and a metamizole metabolite in swine muscle was developed using liquid chromatography-electrospray ionisation-tandem mass spectrometry (LC-ESI-MS/MS). The samples were extracted with acetonitrile (ACN) in solid-liquid extraction followed by a low-temperature partitioning (LLE-LTP) process at -20 ± 2°C. After evaporation to dryness, the residue was reconstituted with hexane and a mixture of water:acetonitrile (1:1). LC separation was achieved on a reversed-phase (RP18) column with gradient elution using water (phase A) and ACN (phase B) both containing 1 mmol l(-)(1) ammonium acetate (NH4COO) with 0.025% acetic acid. Analysis was carried out on a triple-quadrupole tandem mass spectrometer (LC-MS/MS) in multiple reaction monitoring mode using an electrospray interface in negative and positive mode in a single run. Method validation was performed according to the criteria of Commission Decision No. 2002/657/EC. The matrix effect and linearity were evaluated. Decision limit (CCα), detection capability (CCβ), accuracy and repeatability of the method are also reported. The proposed method proved to be simple, easy and adequate for high-throughput analysis and was applied to routine analysis by the Brazilian Ministry of Agriculture, Livestock and Food Supply. PMID:27268755

  2. Multi-residue method for the determination of pesticides and pesticide metabolites in honeybees by liquid and gas chromatography coupled with tandem mass spectrometry--Honeybee poisoning incidents.

    PubMed

    Kiljanek, Tomasz; Niewiadowska, Alicja; Semeniuk, Stanisław; Gaweł, Marta; Borzęcka, Milena; Posyniak, Andrzej

    2016-02-26

    A method for the determination of 200 pesticides and pesticide metabolites in honeybee samples has been developed and validated. Almost 98% of compounds included in this method are approved to use within European Union, as active substances of plant protection products or veterinary medicinal products used by beekeepers to control mites Varroa destructor in hives. Many significant metabolites, like metabolites of imidacloprid, thiacloprid, fipronil, methiocarb and amitraz, are also possible to detect. The sample preparation was based on the buffered QuEChERS method. Samples of bees were extracted with acetonitrile containing 1% acetic acid and then subjected to clean-up by dispersive solid phase extraction (dSPE) using a new Z-Sep+ sorbent and PSA. The majority of pesticides, including neonicotionoids and their metabolites, were analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) but some of pesticides, especially pyrethroid insecticides, were analyzed by gas chromatography tandem mass spectrometry (GC-MS/MS). The procedure was validated according to the Guidance document SANCO/12571/2013 at four concentration levels: 1, 5, 10 and 100 ng/g bees and verified in the international proficiency test. The analysis of bee samples spiked at the limit of quantification (LOQ) showed about 98% mean recovery value (trueness) and 97% of analytes showed recovery in the required range of 70-120% and RSDr (precision) below 20%. Linearity and matrix effects were also established. The LOQs of pesticides were in the range of 1-100 ng/g. The developed method allows determination of insecticides at concentrations of 10 ng/g or less, except abamectin and tebufenozide. LOQ values are lower than the median lethal doses LD50 for bees. The method was used to investigate more than 70 honeybee poisoning incidents. Data about detected pesticides and their metabolites are included. PMID:26830634

  3. Validation of a multi-residue liquid chromatography-tandem mass spectrometry confirmatory method for 10 anticoccidials in eggs according to Commission Decision 2002/657/EC.

    PubMed

    Dubreil-Chéneau, Estelle; Bessiral, Mélaine; Roudaut, Brigitte; Verdon, Eric; Sanders, Pascal

    2009-11-13

    A liquid chromatography-tandem mass spectrometric (LC-MS/MS) method for the simultaneous detection and confirmation of halofuginone, robenidine, diclazuril, nicarbazin, monensin, narasin, lasalocid, salinomycin, maduramicin and semduramicin in whole egg has been developed and validated. The anticoccidial residues were extracted by acetonitrile, evaporated and dissolved in a sodium acetate/acetonitrile mixture. Then, the samples were injected on a C8 column in a gradient mode. Diclazuril-bis, DNC-d8 and nigericin were used as internal standards. The results of the full validation in accordance with the guidelines of the Commission Decision no 2002/657/EC are presented. This rapid and sensitive method was found suitable to confirm the anticoccidials at 1 and at 75 microg kg(-1) for the MRL compound lasalocid. PMID:19442981

  4. A multi-residue method for pesticides analysis in green coffee beans using gas chromatography-negative chemical ionization mass spectrometry in selective ion monitoring mode.

    PubMed

    Pizzutti, Ionara R; de Kok, Andre; Dickow Cardoso, Carmem; Reichert, Bárbara; de Kroon, Marijke; Wind, Wouter; Weber Righi, Laís; Caiel da Silva, Rosselei

    2012-08-17

    In this study, a new gas chromatography-mass spectrometry (GC-MS) method, using the very selective negative chemical ionization (NCI) mode, was developed and applied in combination with a modified acetonitrile-based extraction method (QuEChERS) for the analysis of a large number of pesticide residues (51 pesticides, including isomers and degradation products) in green coffee beans. A previously developed integrated sample homogenization and extraction method for both pesticides and mycotoxins analysis was used. An homogeneous slurry of green milled coffee beans and water (ratio 1:4, w/w) was prepared and extracted with acetonitrile/acetic acid (1%), followed by magnesium sulfate addition for phase separation. Aliquots from this extract could be used directly for LC-MS/MS analysis of mycotoxins and LC-amenable pesticides. For GC-MS analysis, a further clean-up was necessary. C18- and PSA-bonded silica were tested as dispersive solid-phase extraction (d-SPE) sorbents, separate and as a mixture, and the best results were obtained using C18-bonded silica. For the optimal sensitivity and selectivity, GC-MS detection in the NCI-selected ion monitoring (SIM) mode had to be used to allow the fast analysis of the difficult coffee bean matrix. The validation was performed by analyzing recovery samples at three different spike concentrations, 10, 20 and 50 μg kg(-1), with 6 replicates (n=6) at each concentration. Linearity (r(2)) of calibration curves, estimated instrument and method limits of detection and limits of quantification (LOD(i), LOD(m), LOQ(i) and LOQ(m), respectively), accuracy (as recovery %), precision (as RSD%) and matrix effects (%) were determined for each individual pesticide. From the 51 analytes (42 parent pesticides, 4 isomers and 5 degradation products) determined by GC-MS (NCI-SIM), approximately 76% showed average recoveries between 70-120% and 75% and RSD ≤ 20% at the lowest spike concentration of 10 μg kg(-1), the target method LOQ. For the

  5. Multi-residue method for trace level determination of pharmaceuticals in solid samples using pressurized liquid extraction followed by liquid chromatography/quadrupole-linear ion trap mass spectrometry.

    PubMed

    Jelić, Aleksandra; Petrović, Mira; Barceló, Damià

    2009-11-15

    A simple and sensitive method for simultaneous analysis of 43 pharmaceutical compounds in sewage sludge and sediment samples was developed and validated. The target compounds were extracted using pressurized liquid extraction (PLE) and then purified and pre-concentrated by solid phase extraction (SPE) using a hydrophilic-lipophilic balanced polymer. PLE extraction was performed on temperature of 100 degrees C, with methanol/water mixture (1/2, v/v) as extraction solvent. The quantitative analysis was performed by liquid chromatography tandem mass spectrometry using a hybrid triple quadrupole-linear ion trap mass spectrometer (LC-QqLIT-MS). Data acquisition was carried out in selected reaction monitoring (SRM) mode, monitoring two SRM transitions to ensure an accurate identification of target compounds in the samples. Additional identification and confirmation of target compounds were performed using the Information Dependent Acquisition (IDA) function. The method was validated through the estimation of the linearity, sensitivity, repeatability, reproducibility and matrix effects. The internal standard approach was used for quantification because it efficiently corrected matrix effects. Despite the strong matrix interferences, the recoveries were generally higher of 50% in both matrixes and the detection and quantification limits were very low. Beside the very good sensitivity provided by LC-QqLIT-MS, an important characteristic of the method is that all the target compounds can be simultaneously extracted, treated and analysed. Hence, it can be used for routine analysis of pharmaceuticals providing large amount of data. The method was applied for the analysis of pharmaceuticals in river sediment and wastewater sludge from three treatment plants with different treatment properties (i.e. capacity, secondary treatment, quality of influent waters). The analysis showed a widespread occurrence of pharmaceuticals in the sludge matrices. PMID:19782237

  6. Development and validation of a multi-residue liquid chromatography-tandem mass spectrometry confirmatory method for eleven coccidiostats in eggs.

    PubMed

    Galarini, Roberta; Fioroni, Laura; Moretti, Simone; Pettinacci, Laura; Dusi, Guglielmo

    2011-08-26

    A confirmatory method for the determination of residues of eleven coccidiostats including ionophore antibiotics: lasalocid, maduramycin, monensin, narasin, salinomycin, semduramycin and chemical coccidiostats: decoquinate, diclazuril, halofuginone, nicarbazin and robenidine in poultry eggs was developed and validated. The sample was extracted with acetonitrile, defatted with hexane and cleaned-up on a silica SPE cartridge. The analytes were identified and quantified by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The method performance characteristics required by Commission Decision 2002/657/EC were estimated adopting a more flexible and simple validation design. In this alternative approach the experimental study focuses on a larger dynamic range with progressively increasing validation levels. Each of them presents equal concentrations of all the analytes. On the contrary the classical Decision plan investigates a restricted concentration range necessarily different for each analyte being determined by the individual permitted limit (0.5-1.5 times the permitted limit). As a consequence each validation level involves the simultaneous fortification with complex mixtures containing different concentrations of each analyte. Adopting this alternative strategy the validation of several substances with significantly different permitted limits is considerably simplified and a deeper knowledge of the method is achieved. The results proved that the method enables the confirmation of regulated coccidiostats in eggs at the levels required in the official control of residues (CCα in the range of 2.2-174 μg kg(-1), depending on the coccidiostat). The repeatability (CV(r) in the range of 1.1-19%) and within-laboratory reproducibility (CV(Rw) in the range of 1.8-30%) are also acceptable. The procedure was successfully verified in the proficiency test and implemented in the national residue control plan. PMID:21742129

  7. Development and application of a multi-residue method for the determination of 53 pharmaceuticals in water, sediment, and suspended solids using liquid chromatography-tandem mass spectrometry.

    PubMed

    Aminot, Yann; Litrico, Xavier; Chambolle, Mélodie; Arnaud, Christine; Pardon, Patrick; Budzindki, Hélène

    2015-11-01

    Comprehensive source and fate studies of pharmaceuticals in the environment require analytical methods able to quantify a wide range of molecules over various therapeutic classes, in aqueous and solid matrices. Considering this need, the development of an analytical method to determine 53 pharmaceuticals in aqueous phase and in solid matrices using a combination of microwave-assisted extraction, solid phase extraction, and liquid chromatography coupled with tandem mass spectrometry is reported. Method was successfully validated regarding linearity, repeatability, and overall protocol recovery. Method detection limits (MDLs) do not exceed 1 ng L(-1) for 40 molecules in aqueous matrices (6 ng L(-1) for the 13 remaining), while subnanogram per gram MDLs were reached for 38 molecules in solid phase (29 ng g(-1) for the 15 remaining). Losses due to preparative steps were assessed for the 32 analytes associated to their labeled homologue, revealing an average loss of 40 % during reconcentration, the most altering step. Presence of analytes in wastewater treatment plant (WWTP) effluent aqueous phase and suspended solids (SS) as well as in river water, SS, and sediments was then investigated on a periurban river located in the suburbs of Bordeaux, France, revealing a major contribution of WWTP effluent to the river contamination. Sorption on river SS exceeded 5 % of total concentration for amitriptyline, fluoxetine, imipramine, ritonavir, sildenafil, and propranolol and appeared to be submitted to a seasonal influence. Sediment contamination was lower than the one of SS, organic carbon content, and sediment fine element proportion was accountable for the highest measured concentrations. PMID:26353747

  8. Multi-residue analysis method for analysis of pharmaceuticals using liquid chromatography-time of flight/mass spectrometry (LC-TOF/MS) in water sample

    NASA Astrophysics Data System (ADS)

    Al-Qaim, Fouad Fadhil; Abdullah, Md Pauzi; Othman, Mohamed Rozali

    2013-11-01

    In this work, a developed method using solid - phase extraction (SPE) followed by liquid chromatography - time of flight mass spectrometry (LC-ESI-TOF/MS) was developed and validated for quantification and confirmation of eleven pharmaceuticals with different therapeutic classes in water samples, Malaysia. These compounds are caffeine (CAF), prazosin (PRZ), enalapril (ENL), carbamazepine (CBZ), nifedipine (NFD), levonorgestrel (LNG), simvastatin (SMV), hydrochlorothiazide (HYD), gliclazide (GLIC), diclofenac-Na (DIC-Na) and mefenamic acid (MEF). LC was performed on a Dionex Ultimate 3000/LC 09115047 (USA) system. Chromatography was performed on a Thermo Scientific C18 (250 mm × 2.1 mm, i.d.: 5μm) column. Several parameters were optimised such as; mobile phase, gradient elution, collision energy and solvent elution for extraction of compounds from water. The recoveries obtained ranged from 30-148 % in river water. Five pharmaceutical compounds were detected in the surface water samples: caffeine, prazosin, enalpril, diclofenac-Na and mefenamic acid. The developed method is precise and accepted recoveries were got. In addition, this method is suitable to identify and quantify trace concentrations of pharmaceuticals in surface water.

  9. Evaluation and validation of a multi-residue method based on biochip technology for the simultaneous screening of six families of antibiotics in muscle and aquaculture products.

    PubMed

    Gaudin, Valérie; Hedou, Celine; Soumet, Christophe; Verdon, Eric

    2016-01-01

    The Evidence Investigator™ system (Randox, UK) is a biochip and semi-automated system. The microarray kit II (AM II) is capable of detecting several compounds belonging to different families of antibiotics: quinolones, ceftiofur, thiamphenicol, streptomycin, tylosin and tetracyclines. The performance of this innovative system was evaluated for the detection of antibiotic residues in new matrices, in muscle of different animal species and in aquaculture products. The method was validated according to the European Decision No. EC/2002/657 and the European guideline for the validation of screening methods, which represents a complete initial validation. The false-positive rate was equal to 0% in muscle and in aquaculture products. The detection capabilities CCβ for 12 validated antibiotics (enrofloxacin, difloxacin, ceftiofur, desfuroyl ceftiofur cysteine disulfide, thiamphenicol, florfenicol, tylosin, tilmicosin, streptomycin, dihydrostreptomycin, tetracycline, doxycycline) were all lower than the respective maximum residue limits (MRLs) in muscle from different animal origins (bovine, ovine, porcine, poultry). No cross-reactions were observed with other antibiotics, neither with the six detected families nor with other families of antibiotics. The AM II kit could be applied to aquaculture products but with higher detection capabilities from those in muscle. The detection capabilities CCβ in aquaculture products were respectively at 0.25, 0.10 and 0.5 of the respective MRL in aquaculture products for enrofloxacin, tylosin and oxytetracycline. The performance of the AM II kit has been compared with other screening methods and with the performance characteristics previously determined in honey. PMID:26612266

  10. Development of a multi-residue method for the determination of organic micropollutants in water, sediment and mussels using gas chromatography-tandem mass spectrometry.

    PubMed

    Sánchez-Avila, Juan; Fernandez-Sanjuan, María; Vicente, Joana; Lacorte, Silvia

    2011-09-23

    This study describes the development of a multiresidue method based on gas chromatography-electron ionization-tandem mass spectrometry (GC-EI-MS/MS) for the detection of sixteen polycyclic aromatic hydrocarbons (PAHs), five phthalate esters (PEs), seven polychlorinated biphenyls (PCBs), six polybrominated diphenyl ethers (PBDEs), six alkylphenols (APs), three organochlorined pesticides and their isomers or degradation products (OCPs) and bisphenol A in seawater, river water, wastewater treatment plant (WWTP) effluents, sediments and mussels. Solid phase extraction (SPE) was used for the extraction of target analytes in aqueous samples, and ultrasound assisted extraction for solid samples. GC-EI-MS/MS acquisition conditions in selected reaction monitoring (SRM) using two transitions per compound were optimized. In this way, quantification and unequivocal identification of organic micropollutants were performed in compliance with the Decision 2002/657/EC. Good linearity responses with coefficients of determination higher than 0.99 were obtained. Methodological detection limits (MDLs) in seawater ranged from 0.1 to 6 ng L(-1); in river water from 0.1 to 4.8 ng L(-1); in WWTP effluents from 1 to 75 ng L(-1); in sediments from 1 to 150 ng g(-1) and in mussels from 1 to 125 ng g(-1). MDLs and recovery yields were compared with other published methods and similarities or even improvements were achieved. The optimized method was applied to analyze five samples from each matrix collected in coastal areas, showing its potential use for marine pollution monitoring. PMID:21824622

  11. Miniaturisation and optimisation of the Dutch mini-Luke extraction method for implementation in the routine multi-residue analysis of pesticides in fruits and vegetables.

    PubMed

    Lozano, Ana; Kiedrowska, Barbara; Scholten, Jos; de Kroon, Marijke; de Kok, André; Fernández-Alba, Amadeo R

    2016-02-01

    This paper presents the validation and further miniaturisation of the well-known Dutch mini-Luke method for high water and acid content matrices for 175 pesticides amenable to liquid- and gas chromatography-mass spectrometry. For optimisation of the method, recovery tests with different sample/extraction solvent ratios, varying amounts of dichloromethane and salts were performed with fifty representative pesticides. Solvent consumption could be reduced considerably, especially for the dichloromethane (by a factor of 3). Recovery studies performed with lettuce and orange matrix spiked at 0.005, 0.01 and 0.02 mg/kg yielded average recoveries in the range 70-120% with relative standard deviation values below 20% for almost all the pesticides tested. The linearity over three orders of magnitude was demonstrated (r(2) > 0.99). The matrix effect could be considered as not significant. The limit of quantification was 0.005 mg/kg for 96% of the compounds. The optimised New Dutch mini-Luke ("NL"-) method was applied successfully in routine analysis and the EUPT FV-16 sample. PMID:26304397

  12. Multi-residue method for the confirmation of four avermectin residues in food products of animal origin by ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Wang, Fengmei; Chen, Junhui; Cheng, Hongyan; Tang, Zhixu; Zhang, Gang; Niu, Zengyuan; Pang, Shiping; Wang, Xiaoru; Lee, Frank Sen-Chun

    2011-05-01

    A confirmatory method was developed for the rapid determination of abamectin, ivermectin, doramectin and eprinomectin residues in various food products of animal origin, such as pork muscle, pork liver, fish and milk. Samples were homogenized, extracted and de-proteinized by acetonitrile, cleaned via two-step cleaning procedure using Bond Elut C(18) SPE columns and then alumina-N cartridges. All the four avermectin residues in different animal-food products were simultaneously separated and determined by ultra-performance liquid chromatography-electrospray ionization tandem mass spectrometry (UPLC-ESI-MS/MS) within 3.5 min. Data acquisition under positive ESI-MS/MS was performed by applying multiple reaction monitoring (MRM) for both identification and quantification, and mass spectrometric conditions were optimized to increase selectivity and sensitivity. The matrix-matched calibration curves for different matrices, such as pork muscle, pork liver, fish and milk, were constructed and the interference effect of different sample matrices on the ionization was effectively eliminated. The UPLC-MS/MS method was validated with satisfactory linearity, recovery, precision and stability. Matrix-matched calibration curves of abamectin, ivermectin, doramectin and eprinomectin in four different matrices were linear (r(2)( )≥ 0.990, goodness-of-fit coefficients ≤12.8%) in the range 2.5-200 µg kg(-1). The limits of detection and quantification for the four avermectins were in the range 0.05-0.68 and 0.17-2.27 µg kg(-1), respectively. Recoveries were 62.4-104.5% with good intra- and inter-day precision. The method was rapid, sensitive and reliable, and can be applied to the quantitative analysis of avermectin residues in different animal-food products. PMID:21598143

  13. Multi-residue method for determination of selected neonicotinoid insecticides in honey using optimized dispersive liquid-liquid microextraction combined with liquid chromatography-tandem mass spectrometry.

    PubMed

    Jovanov, Pavle; Guzsvány, Valéria; Franko, Mladen; Lazić, Sanja; Sakač, Marijana; Šarić, Bojana; Banjac, Vojislav

    2013-07-15

    The objective of this study was to develop analytical method based on optimized dispersive liquid-liquid microextraction (DLLME) as a pretreatment procedure combined with reversed phase liquid chromatographic separation on C18 column and isocratic elution for simultaneous MS/MS determination of selected neonicotinoid insecticides in honey. The LC-MS/MS parameters were optimized to unequivocally provide good chromatographic separation, low detection (LOD, 0.5-1.0 μg kg(-1)) and quantification (LOQ, 1.5-2.5 μg kg(-1)) limits for acetamiprid, clothianidin, thiamethoxam, imidacloprid, dinotefuran, thiacloprid and nitenpyram in honey samples. Using different types (chloroform, dichloromethane) and volumes of extraction (0.5-3.0 mL) and dispersive (acetonitrile; 0.0-1.0 mL) solvent and by mathematical modeling it was possible to establish the optimal sample preparation procedure. Matrix-matched calibration and blank honey sample spiked in the concentration range of LOQ-100.0 μg kg(-1) were used to compensate the matrix effect and to fulfill the requirements of SANCO/12495/2011 for the accuracy (R 74.3-113.9%) and precision (expressed in terms of repeatability (RSD 2.74-11.8%) and within-laboratory reproducibility (RSDs 6.64-16.2%)) of the proposed method. The rapid (retention times 1.5-9.9 min), sensitive and low solvent consumption procedure described in this work provides reliable, simultaneous, and quantitative method applicable for the routine laboratory analysis of seven neonicotinoid residues in real honey samples. PMID:23622535

  14. Multi-residue method for the detection of veterinary drugs in distillers grains by liquid chromatography-Orbitrap high resolution mass spectrometry.

    PubMed

    Kaklamanos, George; Vincent, Ursula; von Holst, Christoph

    2013-12-27

    Distillers Grain (DG) is an important by-product of ethanol production. The ethanol production process uses only the starch portion of the plant and all the remaining nutrients, protein, fat, minerals, and vitamins remain in DGs, a valuable feed material for livestock. The use of antimicrobial drugs is helpful to limit harmful bacterial growth during the early part of the fermentation process. This can lead to the possible presence of contaminants in the by-products that are used in the food and feed industries, resulting in a major concern for the development of bacterial resistance in both humans and animals. To facilitate the detection of antimicrobial and other commonly used veterinary drugs in DGs, a liquid chromatography-high resolution mass spectrometry (LC-HRMS) method was developed targeting a wide range of 12 chemical classes of anti-bacterial substances and drugs, such as ionophore and non-ionophore authorized coccidiostats, banned coccidiostats, macrolides, tetracyclines, nitroimidazoles, amphenicols, quinolones, sulphonamides, tranquilizers, non-steroidal anti-inflammatory drugs and benzimidazoles. Following a simple and fast extraction step with a mixture of organic solvents, the extract was directly injected into the LC coupled to an Orbitrap mass analyzer. The identification of residues is based on accurate mass measurement. The high mass resolution of 50,000 full width at half maximum (FWHM) and corresponding narrow mass windows permitted a very selective and sensitive detection of the analytes in such a complex matrix. A single-laboratory validation procedure was carried out evaluating selectivity, sensitivity, linearity, precision and accuracy. The method showed satisfactory analytical performance for precision and trueness, and allowed the determination of the compounds at low concentration. The proposed multi-method demonstrated that liquid chromatography coupled to an Orbitrap mass spectrometer is a promising analytical technique, suitable for

  15. Development of a multi-residue method for fast screening and confirmation of 20 prohibited veterinary drugs in feedstuffs by liquid chromatography tandem mass spectrometry.

    PubMed

    Zhang, Gui-Jun; Fang, Bing-Hu; Liu, Ya-Hong; Wang, Xu-Feng; Xu, Li-Xiao; Zhang, Ya-Ping; He, Li-Min

    2013-10-01

    A simple multiresidue method was developed for detecting and quantifying twenty analytes from 5 classes of prohibited veterinary drugs (β-agonists (9), anabolic hormones (4), quinoxalines (4), tranquilizers (1), cyproheptadine, and clonidine in animal feeds using a QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach. Feed samples were extracted by ultrasonic-assisted extraction with a mixture of methanol-acetonitrile (50:50, v/v), followed by a cleanup using a dispersive solid-phase extraction with PSA (primary secondary amine). Target compounds were separated and determined by a liquid chromatography tandem quadrupole mass spectrometer operating in positive electrospray ionization mode, using multiple reaction monitoring (MRM). The recoveries of these compounds were between 56.7% and 103% at three spiked levels. The repeatability was lower than 10%, whereas reproducibility was no more than 15% except for nandrolone (17% at 10μgkg(-1)) and diazepam (19% at 10μgkg(-1)). Decision limits (CCαs) and detection capabilities (CCβs) ranged from 0.42 to 5.74μgkg(-1) and 5.70-9.81μgkg(-1), respectively. The method was successfully applied to screening of real samples obtained from local feed markets and confirmation of the suspected target analytes. PMID:23962505

  16. The comparison of dispersive solid phase extraction and multi-plug filtration cleanup method based on multi-walled carbon nanotubes for pesticides multi-residue analysis by liquid chromatography tandem mass spectrometry.

    PubMed

    Qin, Yuhong; Zhao, Pengyue; Fan, Sufang; Han, Yongtao; Li, Yanjie; Zou, Nan; Song, Shuangyu; Zhang, Yuan; Li, Fangbing; Li, Xuesheng; Pan, Canping

    2015-03-13

    In this study, dispersive-Solid Phase Extraction (d-SPE) cleanup and multi-plug filtration cleanup (m-PFC) methods were compared for 25 representative pesticides in six matrices (wheat, spinach, carrot, apple, citrus and peanut) by QuEChERS-LC-ESI-MS/MS detection. The type of sorbents in dispersive-SPE (d-SPE) was optimized for the above matrices. Multi-walled carbon nanotubes (MWCNTs), which mixed other materials like PSA (Primary Secondary Amines), GCB (Graphitized Carbon Black) and C18 (Octadecyl-silica), showed brilliant cleanup performance in multi residue monitoring (MRM) pesticide residue analysis. Cleanup effects with d-SPE and m-PFC methods were examined. When spiked at 3 concentration levels of 10, 100, 500 μg/kg in above matrices, for both d-SPE and m-PFC methods, the recoveries ranged from 70 to 110% with relative standard deviations (RSDs) lower than 20%. Limits of quantification (LOQs) for both cleanup methods ranged from 1 to 25 μg/kg. Matrix-matched calibrations were performed with the coefficients of determination more than 0.99 between concentration levels of 10-1000 μg/kg. It was found that m-PFC was more convenient and effective than d-SPE with the same sorbents, due to the increased contact time and contact area between the extracts and compressed sorbents. The study demonstrated that m-PFC method could be used as a rapid, convenient and high-throughput cleanup method for analysis of pesticide residues. PMID:25660523

  17. A multi-residue method for characterization and determination of atmospheric pesticides measured at two French urban and rural sampling sites.

    PubMed

    Baraud, Laurent; Tessier, Didier; Aaron, Jean-Jacques; Quisefit, Jean-Paul; Pinart, Johann

    2003-12-01

    The extensive use of pesticides to protect agricultural crops can result in the transfer of these compounds into the atmosphere and their diffusion towards urban areas. Precise evaluation of the geographic impact of this type of pollution is important environmentally. In this paper, analytical methods for the sampling, characterization, and determination of agricultural pesticides in air were developed; the methods were then applied in the Paris and Champagne regions. Sixteen pesticides belonging to nine chemical families were monitored. Sampling was carried out in urban (Paris) and rural (Aube district) sites, utilizing either a high-volume pump (12.5 m3 h(-1)) (urban site) or a low-volume pump (2.3 m3 h(-1)) for the rural site. Quartz filters and polyurethane foams (PUF) were used for sampling in all cases. After extracting the samples and concentrating the recovered solutions, high-performance liquid chromatography (HPLC) analysis with UV detection was performed. Identification of the pesticides was confirmed by applying to the HPLC measurements a novel UV-detection procedure based on the normalized absorbance variation with wavelength (Noravawa procedure). The presence of metsulfuron methyl, isoproturon, linuron, deltamethrin (and/or malathion), and chlorophenoxy acids (2,4-D and MCPP) was found at the urban sampling site at levels ranging from about 1 to 1130 ng m(-3) of air, depending on the compound and sampling period. On the rural sampling site residues of isoproturon, deltamethrin (and/or malathion), MCPP, and 2,4-D were generally detected at higher levels (19-5130 ng m(-3)) than on the urban site, as expected. The effects of the weather conditions and agricultural activity on the atmospheric concentrations of pesticides are discussed, as are long-range atmospheric transfer processes for these pesticides. PMID:13680058

  18. Rapid multi-residue method for the quantitative determination and confirmation of glucocorticosteroids in bovine milk using liquid chromatography-electrospray ionization-tandem mass spectrometry.

    PubMed

    McDonald, Mark; Granelli, Kristina; Sjöberg, Pernilla

    2007-04-01

    Dexamethasone, betamethasone and prednisolone are synthetic glucocorticosteroids authorized for therapeutic use in bovine animals within the European Union. Dexamethasone and betamethasone are used mainly for the treatment of metabolic and inflammatory diseases. Prednisolone is used to treat bovine mastitis. Maximum residue limits (MRLs) of 0.3 microg kg(-1) for both dexamethasone and betamethasone and 6.0 microg kg(-1) for prednisolone in bovine milk have been established. 6alpha-Methylprednisolone and flumethasone are not authorized for use in bovine animals and are completely banned in bovine milk. The proposed method is based on deprotenisation of milk using 20% (w/v) trichloroacetic acid. Samples are filtered using glass microfiber filters and subject to clean-up using OASIS HLB solid phase extraction. Separation was achieved on a Hypercarb 100 mm x 2.1 mm x 5 microm column. Mobile phase was: 90/10 acetonitrile/0.1% formic acid in water; flow rate was 600 microL min(-1). The method allowed the rapid identification and confirmation of the five glucocorticosteroids according to the criteria laid down in Commission Decision 2002/657/EC. Matrix calibration curves for all compounds were linear in the interval 0.0 MRL to 2.0 MRL with a correlation coefficient (r(2)) higher than 0.96. Relative recoveries ranged from 97% for betamethasone to 111% for prednisolone. Precision at the MRL ranged from 3.8% for prednisolone to 13.8% for betamethasone. Decision limits, CCalpha, and detection capability, CCbeta have been calculated for all compounds. PMID:17386789

  19. A simple and rapid screening method for sulfonamides in honey using a flow injection system coupled to a liquid waveguide capillary cell.

    PubMed

    Catelani, Tiago Augusto; Tóth, Ildikó Vargáné; Lima, José L F C; Pezza, Leonardo; Pezza, Helena Redigolo

    2014-04-01

    A rapid and simple screening method was developed for the determination of sulfonamides in honey samples by flow injection analysis (FIA) coupled to a liquid waveguide capillary cell. The proposed method is based on the reaction between sulfonamides and p-dimethylaminocinnamaldehyde (p-DAC) in the presence of sodium dodecylsulate (SDS) in dilute acid medium (hydrochloric acid), with the reaction product being measured spectrophotometrically at λ(max) = 565 nm. Experimental design methodology was used to optimize the analytical conditions. The proposed technique was applied to the determination of sulfonamides (sulfaquinoxaline, sulfadimethoxine, and sulfathiazole) in honey samples, in a concentration range from 6.00 × 10(-3) to 1.15 × 10(-1)mg L(-1). The detection (LOD) and quantification (LOQ) limits were 1.66 × 10(-3) and 5.54 × 10(-3)mg L(-1), respectively. Positive and false positive samples were also analyzed by a confirmatory HPLC method. The proposed system enables the screening of sulfonamides in honey samples with a low number of false positive results, with fast response therefore offers a new tool for consumer protection. PMID:24607139

  20. A multi-residue method for the determination of pesticides in high water content matrices by gas chromatography-single quadrupole mass spectrometry with electron ionisation (EI-GC/MS).

    PubMed

    de Oliveira, Mauro Lúcio Gonçalves; Madureira, Fernando Diniz; Aurélio, Fabiano; Pontelo, Ana Paula; Silva, Gilsara; Oliveira, Reginaldo; Paes, Cláudia

    2012-01-01

    An EI-GC/MS method for the determination of pesticide residues in vegetable matrices with high water content was validated using papaya samples. The validation of a multi-residue pesticide method was in agreement with national and international regulations enabling the Ministry of the Agriculture, Livestock and Food Supply of Brazil to cover a large number of matrices and pesticide residues in its monitoring and control programmes. The extraction used 60 mL of ethyl acetate and 30 g of sample previously processed. After extraction, clean-up of all the extracts was carried out by percolation through GBC cartridges. The samples were then injected in an EI-GC/MS system. Calibration curves were prepared in quadruplet by fortifying blank extracts with a standard solution containing all the pesticides studied at 0.000, 0.005, 0.010, 0.020, 0.030, 0.050, 0.080 and 0.100 mg kg(-1). For the recovery study, blank samples were fortified at 0.010, 0.020, 0.030, 0.050 and 0.080 mg kg(-1) and then submitted to the extraction procedure. The complete procedure was repeated over four different days by two analysts. The regression parameters of calibration curves were calculated for each validation day. Linearity, selectivity, specificity, robustness, limits of detection and quantification were also assessed. The uncertainty was estimated for each analyte at each spike level studied. The method had recoveries between 91% and 105% and precision results ≤ 20%. Limits of quantification were below or equal to the maximum residue limits (MRLs) regulated by Brazilian legislation. The MRLs of the selected pesticides are not regulated by CODEX Alimentarius. The results are also in agreement with SANCO/10684/2009. PMID:22292605

  1. Rapid multi-residue method for the determination of azinphos methyl, bromopropylate, chlorpyrifos, dimethoate, parathion methyl and phosalone in apricots and peaches by using negative chemical ionization ion trap technology.

    PubMed

    Liapis, Konstantinos S; Aplada-Sarlis, Pipina; Kyriakidis, Nikolaos V

    2003-05-01

    A rapid, selective and sensitive multi-residue method for the determination of six common pesticides in stone fruit samples is described. The proposed method involves the extraction of the pesticides with the use of acetone solvent followed by liquid-liquid partition with a mixture of dichloromethane and light petroleum (40-60 degrees C) and subsequent determination by a gas chromatographic-mass spectrometry system using ion trap technology in negative ion chemical ionization mode. The average percent recoveries of bromopropylate and phosalone in the concentration range 0.2-2.0 mg/kg were 97.3 +/- 6.7 to 120 +/- 1.0%, while the recoveries of chlorpyrifos and parathion methyl examined in the concentration range 0.02-0.2 mg/kg were 95.5 +/- 7.5 to 145 +/- 3.6%, the recoveries of azinphos methyl in the range 0.05-0.5 mg/kg were 74.8 +/- 29.6 to 96.5 +/- 13% and those of dimethoate in the range 0.1-1.0 mg/kg were 73.1 +/- 5.7 to 92.8 +/- 2.8% for n = 3 for all the above pesticides. The high mean recovery (145%) for chlorpyrifos is attributed to a matrix enhancement effect. The limits of quantitation in apricots were 0.01 mg/kg for chlorpyrifos, 0.02 mg/kg for dimethoate and parathion methyl, 0.05 mg/kg for azinphos methyl and phosalone and 0.1 mg/kg for bromopropylate. The usefulness of tandem mass spectrometry for confirmation purposes was also examined. The method was applied successfully to the determination of the target pesticides in 32 samples of stone fruits (apricots and peaches). PMID:12830919

  2. Development of a multi-residue method for the determination of pesticides in cereals and dry animal feed using gas chromatography-tandem quadrupole mass spectrometry II. Improvement and extension to new analytes.

    PubMed

    Walorczyk, Stanisław

    2008-10-24

    This paper describes the extension and re-validation of a previously published multi-residue method to currently 140 pesticides and 4 pesticide degradation products in cereals and feedingstuffs. The pesticides were extracted using buffered QuEChERS ("quick, easy, cheap, rugged, effective and safe") method and then cleaned up using dispersive solid-phase extraction with Bondesil PSA and C18 sorbents, and optionally by a freezing-out clean-up step. The final extracts were analyzed in a single injection gas chromatographic-tandem quadrupole mass spectrometric (GC-MS/MS) acquisition method. A high degree of confidence was achieved by entering two multiple reaction monitoring transitions per compound. In this way, quantification of analytical results and unequivocal identification of pesticide residues in compliance with the recent European Union criteria could be done in a single analysis. Thorough optimization of the GC-MS/MS acquisition conditions and application of an effective clean-up procedure has resulted in a remarkable enhancement of the validation parameters. The linearity of the calibration curves was excellent in matrix-matched standards, and yielded the coefficients of determination (R(2))> or =0.99 for approximately 96% of the target analytes. Average recoveries of the pesticides spiked at 0.01mgkg(-1) into a feed mixture and wheat grain were in the range 70-120% with associated RSD values < or =20% for approximately 60% and 67% of the compounds, respectively. At the higher spiking levels of 0.05, 0.1 and 0.5mgkg(-1) average recoveries and RSDs readily met the validation criteria for nearly all the studied pesticides. Based on these results, the proposed approach has been proven to be highly efficient and suitable for routine determinations of multi-class pesticides in a range of cereal and related matrices. Up to now, 145 samples of matrices of differing complexity including cereals grain, bran, whole ears, straw, hay, feed mixtures and other samples

  3. Synthesis of Aryl Sulfonamides via Palladium-Catalyzed Chlorosulfonylation of Arylboronic Acids

    PubMed Central

    DeBergh, J. Robb; Niljianskul, Nootaree; Buchwald, Stephen L.

    2013-01-01

    A palladium-catalyzed method for the preparation of sulfonamides is described. The process exhibits significant functional group tolerance and allows for the preparation of a number of arylsulfonyl chlorides and sulfonamides under mild conditions. PMID:23837740

  4. One-Step Synthesis of Sulfonamides from N-Tosylhydrazones.

    PubMed

    Tsai, Andy S; Curto, John M; Rocke, Benjamin N; Dechert-Schmitt, Anne-Marie R; Ingle, Gajendrasingh K; Mascitti, Vincent

    2016-02-01

    The first described reaction between N-tosylhydrazone and SO2 is reported to provide alkyl sulfonamides in the presence of various amines. In this procedurally simple method, hydrazones of both unsaturated aldehydes and ketones proceed in moderate to excellent yields. Primary and secondary aliphatic amines are accommodated in this reaction, which provides a novel route to sulfonamides. PMID:26771228

  5. Multiresidue analysis of sulfonamides in meat by supramolecular solvent microextraction, liquid chromatography and fluorescence detection and method validation according to the 2002/657/EC decision.

    PubMed

    Costi, Esther María; Sicilia, María Dolores; Rubio, Soledad

    2010-10-01

    A multiresidue method was described for determining eight sulfonamides, SAs (sulfadiazine, sulfamerazine, sulfamethoxypyridazine, sulfachloropyridazine, sulfadoxine, sulfamethoxazole, sulfadimethoxine and sulfaquinoxaline) in animal muscle tissues (pork, chicken, turkey, lamb and beef) at concentrations below the maximum residue limit (100 μg kg(-1)) set by the European Commission. The method was based on the microextraction of SAs in 300-mg muscle samples with 1 mL of a supramolecular solvent made up of reverse micelles of decanoic acid (DeA) and posterior determination of SAs in the extract by LC/fluorescence detection, after in situ derivatization with fluorescamine. Recoveries were quantitative (98-109%) and matrix-independent, no concentration of the extracts was required, the microextraction took about 30 min and several samples could be simultaneously treated. Formation of multiple hydrogen bonds between the carboxylic groups of the solvent and the target SAs (hydrogen donor and acceptor sum between 9 and 11) were considered as the major forces driving microextraction. The method was validated according to the European Union regulation 2002/657/EC. Analytical performance in terms of linearity, selectivity, trueness, precision, stability of SAs, decision limit and detection capability were determined. Quantitation limits for the different SAs ranged between 12 μg kg(-1) and 44 μg kg(-1), they being nearly independent of matrix composition. Repeatability and reproducibility, expressed as relative standard deviation, were in the ranges 1.8-3.6% and 3.3-6.1%. The results of the validation process proved that the method is suitable for determining sulfonamide residues in surveillance programs. PMID:20810118

  6. Development and validation of an HPLC method for the determination of ten sulfonamide residues in milk according to 2002/657/EC.

    PubMed

    Tolika, Evanthia P; Samanidou, Victoria F; Papadoyannis, Ioannis N

    2011-07-01

    A HPLC method with diode-array detection, at 265 nm, was developed and validated for the determination of ten sulfonamides (SAs): sulfadiazine (SDZ), sulfathiazine (STZ), sulfamethoxine (SMTH), sulfamethizole (SMZ), sulfamethoxypyridazine (SMPZ), sulfamonomethoxine (SMMX), sulfamethoxazole (SMXZ), sulfisoxazole (SIX), sulfadimethoxine (SDMX), and sulfaquinoxaline (SQX) in milk. A mixture of ethyl acetate, n-hexane, and isopropanol was used for the extraction of target analytes from milk. The mobile phase, a mixture of 0.1% v/v formic acid, CH(3) CN, and CH(3) OH was delivered to the analytical column under a gradient program. The procedure was validated according to the European Union regulation 2002/657/EC in terms of selectivity, stability, decision limit, detection capability, accuracy, and precision. Mean recoveries of sulfonamides from milk samples spiked at three concentration levels (0.5×MRL, 1×MRL, and 1.5×MRL) (MRL, maximum residue level) were 93.9-115.9% for SDZ, 97.8-102.9% for STZ, 94.6-107.0% for SMTH, 98.3-111.5% for SMZ, 95.3-108.4% for SMPZ, 97.9-106.0% for SMMX, 97.6-111.3% for SMXZ, 94.3-104.6% for SIX, 96.4-109.1% for SDMX, and 98.2-111.2% for SQX. All RSD values were lower than 8.8%. The decision limits CCa calculated by spiking 20 blank milk samples at MRL (100 μg/kg) ranged from 101.61 to 106.84 μg/kg, whereas the detection capability CCb ranged from 105.64 to 119.01 μg/kg. PMID:21644254

  7. Determination of some sulfonamides and trimethoprim in chicken, fish muscle and eggs by liquid chromatography-tandem mass spectrometry.

    PubMed

    Forti, A F; Multari, M; Di Stefano, L; Scortichini, G

    2004-01-01

    Sulfonamides represent a wide range of synthetic compounds commonly used in veterinary therapy for the treatment of several bacterial and protozoan infections in cattle, swine and poultry. Trimethoprim is another antibacterial agent mainly used in fish culture and often combined with sulfonamides in commercial preparations. Residues of these drugs in foodstuffs are of concern because of their potential carcinogenic character. Consequently, the European Union (EU) and United States Food and Drug Administration set maximum residue limits for both sulfonamides (100 microg/kg either as a single molecule or as a sum of all detected compounds within the class) and trimethoprim (TMP) (50 microg and 100 microg/kg, according to the matrix) in chicken, fish muscle and eggs.On the other hand, these limits have made of concern the development of confirmatory methods for the analysis of these molecules. LC-MS/MS technique, in particular, resulted fit for the detection of these medium polarity compounds. An effective multi-residue method is presented for the simultaneous determination of certain sulfonamides (sulfadiazine, sulfathiazole, sulfamerazine, sulfamethazine, sulfamethoxypyridazine, sulfamethoxazole, sulfadimethoxine and sulfaquinoxaline) and TMP in products of animal origin (chicken muscle, fish muscle and eggs) by liquid chromatographymass spectrometry/mass spectrometry (LC-MS/MS) at levels in compliance with the legislation in force. The drugs were extracted with a mixture of dichloromethane/acetone (1:1, v/v) and clean-up was carried out by solid phase extraction (SPE) on a sulfonic acid column after addition of acetic acid to the extract, so as to allow for ionexchange. Sulfonamides and TMP were then eluted from the SPE column using a solution of ammonia in methanol. The chromatographic separation was performed on a C18 column by using a mobile phase of methanol/5 mM aqueous ammonium acetate and 0.1% formic acid in gradient, and the LC-MS/MS analysis was performed

  8. Gradient liquid chromatographic retention time prediction for suspect screening applications: A critical assessment of a generalised artificial neural network-based approach across 10 multi-residue reversed-phase analytical methods.

    PubMed

    Barron, Leon P; McEneff, Gillian L

    2016-01-15

    For the first time, the performance of a generalised artificial neural network (ANN) approach for the prediction of 2492 chromatographic retention times (tR) is presented for a total of 1117 chemically diverse compounds present in a range of complex matrices and across 10 gradient reversed-phase liquid chromatography-(high resolution) mass spectrometry methods. Probabilistic, generalised regression, radial basis function as well as 2- and 3-layer multilayer perceptron-type neural networks were investigated to determine the most robust and accurate model for this purpose. Multi-layer perceptrons most frequently yielded the best correlations in 8 out of 10 methods. Averaged correlations of predicted versus measured tR across all methods were R(2)=0.918, 0.924 and 0.898 for the training, verification and test sets respectively. Predictions of blind test compounds (n=8-84 cases) resulted in an average absolute accuracy of 1.02±0.54min for all methods. Within this variation, absolute accuracy was observed to marginally improve for shorter runtimes, but was found to be relatively consistent with respect to analyte retention ranges (~5%). Finally, optimised and replicated network dependency on molecular descriptor data is presented and critically discussed across all methods. Overall, ANNs were considered especially suitable for suspects screening applications and could potentially be utilised in bracketed-type analyses in combination with high resolution mass spectrometry. PMID:26592605

  9. Multi-residue methods for the determination of over four hundred pesticides in solid and liquid high sucrose content matrices by tandem mass spectrometry coupled with gas and liquid chromatograph.

    PubMed

    Lozowicka, Bozena; Ilyasova, Gulzhakhan; Kaczynski, Piotr; Jankowska, Magdalena; Rutkowska, Ewa; Hrynko, Izabela; Mojsak, Patrycja; Szabunko, Julia

    2016-05-01

    For the first time three methods: matrix solid phase dispersion (MSPD), original and modified QuEChERS, with and without clean up step were studied in order to evaluate the extraction efficiency of various classes of pesticides from solid and liquid high sucrose content matrices. Determinations over four hundred pesticides were performed by gas and liquid chromatography with triple quadrupole mass spectrometry (GC/LC/MS/MS) using multiple reaction monitoring. The proposed methods were validated on sugar beets and their technological product beet molasses. In general, the recoveries obtained for the original QuEChERS and MSPD method were lower (<70%) than for the modified QuEChERS without clean up in sugar beet and with clean up in beet molasses. Among these methods, high extraction yields were achieved as recommended in SANCO/12571/2013, with repeatability of 4.4-19.2% and within-laboratory reproducibility of 7.1-18.4% for citrate QuEChERS, whereas greater ruggedness were observed for MSPD. The limit of quantification (LOQ) at (the lowest MRL=0.01mgkg(-1)e.g. for oxamyl()) or below (0.005mgkg(-1)) the regulatory maximum residue level for the pesticides were achieved. The expanded measurement uncertainty was not higher than 30% for all target analytes. Matrix effects were compared and observed for both matrices at both gas and liquid chromatography. The most compounds showed signal enhancement and it was compensated by using matrix-matched calibration and modified QuEChERS characterized lower matrix effects. The confirmation of suitability citrate QuEChERS optimized method was to use for routine testing of several dozen samples determination and residue of epoxiconazole and tebuconazole (both at 0.01mgkg(-1)) in the samples of beet molasses and cyfluthrin (0.06mgkg(-1)) in sugar beet were found. PMID:26946009

  10. A multi-residue method for the analysis of pesticides and pesticide degradates in water using HLB solid-phase extraction and gas chromatography-ion trap mass spectrometry

    USGS Publications Warehouse

    Hladik, M.L.; Smalling, K.L.; Kuivila, K.M.

    2008-01-01

    A method was developed for the analysis of over 60 pesticides and degradates in water by HLB solid-phase extraction and gas-chromatography/mass spectrometry. Method recoveries and detection limits were determined using two surface waters with different dissolved organic carbon (DOC) concentrations. In the lower DOC water, recoveries and detection limits were 80%-108% and 1-12 ng/L, respectively. In the higher DOC water, the detection limits were slightly higher (1-15 ng/L). Additionally, surface water samples from four sites were analyzed and 14 pesticides were detected with concentrations ranging from 4 to 1,200 ng/L. ?? 2008 Springer Science+Business Media, LLC.

  11. Multi-residue analytical method for the determination of endocrine disruptors and related compounds in river and waste water using dual column liquid chromatography switching system coupled to mass spectrometry.

    PubMed

    Gorga, Marina; Petrovic, Mira; Barceló, Damià

    2013-06-21

    The present study describes a novel, fully automated method, based on column switching using EQuan™ columns for an integrated sample preconcentration and liquid chromatography coupled to tandem mass spectrometry (LC-LC-MS/MS). The method allows the unequivocal identification and quantification of the most relevant environmental endocrine disruptors compounds (EDCs) and compounds suspected to be EDCs, such as natural and synthetic estrogens and their conjugates, antimicrobials, parabens, bisphenol A, alkylphenolic compounds, benzotriazoles, and organophosphorus flame retardants, in surface river water and wastewater samples. Applying this technique, water samples were directly injected into the chromatographic system and the target compounds were concentrated into the loading column. Thereafter, the analytes were transferred into the analytical column for subsequent detection by MS-MS (QqQ). A comparative study employing three types of columns, with different chemical modifications, was performed in order to determine the optimal column that allowed maximum retention and subsequent elution of the analytes. Using this new optimized methodology a fast and easy online methodology for the analysis of EDCs in surface river water and wastewater with low limits of quantification (LOQ) was obtained. LOQs ranged from 0.008 to 1.54 ng/L for surface river water and from 0.178/0.364 to 12.5/25.0 ng/L (except for alkylphenol monoethoxylates) for effluent/influent waste water. Moreover, employing approximately 1h, a complete analysis was performed which was significant improvement in comparison to other methods reported previously. This method was used to track the presence and fate of target compounds in the Ebro River which is the most important river in Spain whose intensive agricultural and industrial activities concentrate mainly close to the main cities in the basin, deteriorating soil and water quality. PMID:23683400

  12. Multi-residue determination of 171 pesticides in cowpea using modified QuEChERS method with multi-walled carbon nanotubes as reversed-dispersive solid-phase extraction materials.

    PubMed

    Han, Yongtao; Song, Le; Zou, Nan; Chen, Ronghua; Qin, Yuhong; Pan, Canping

    2016-09-15

    A rapid and sensitive method for the determination of 171 pesticides in cowpea was developed using multi-walled carbon nanotubes (MWCNTs) as reversed-dispersive solid-phase (r-DSPE) extraction materials. The clean-up performance of MWCNTs was proved to be obviously superior to PSA and GCB. This method was validated on cowpea spiked at 0.01 and 0.1mgkg(-1) with five replicates. The mean recoveries for 169 pesticides ranged from 74% to 129% with relative standard deviations (RSDs) (n=5) lower than 16.4%, except diflufenican and quizalofop-ethyl. Good linearity for all pesticides was obtained with the calibration curve coefficients (R(2)) larger than 0.9970. The limit of detection (LODs) and limit of quantification (LOQs) for the 171 pesticides ranged from 0.001 to 0.003mgkg(-1) and from 0.002 to 0.009mgkg(-1), respectively. The method was demonstrated to be reliable and sensitive for the routine monitoring of the 171 pesticides in cowpea samples. PMID:27475452

  13. Multi-residue Method for Determination of Selected Neonicotinoid Insecticides in Traditional Chinese Medicine Using Modified Dispersive Solid-phase Extraction Combined with Ultra-performance Liquid Chromatography Tandem Mass Spectrometry.

    PubMed

    Qin, Yao; Chen, Lina; Yang, Xiaojing; Li, Sainan; Wang, Yumeng; Tang, Ying; Liu, Chunming

    2015-01-01

    A reliable and cost-effective method for the determination of multiple neonicotinoids was developed using a modified QuEChERS-based extraction procedure in complex matrices, namely Hedyotis diffusa (a representative of the Traditional Chinese herb which contains lots of pigment, saponin and terpene) and Semifluid extract of deer foetus (a representative of the Chinese traditional patent medicine that was produced with several different herbs, and especially containing lots of protein, except for other interference components). Ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) was used for the quantification and confirmation of five compounds. Except for two transitions obtained by the MRM mode, identification was further carried out by the ion radios. The proposed chemical structure of every selected product ion and the proposed pyrolysis way were presented. The extraction, clean-up, UPLC separation and MS/MS parameters were especially optimized in order to obtain better recoveries. The low limits of detection (LODs) of five insecticides ranged from 0.04 to 0.81 μg kg(-1). Matrix matched calibration in the concentration range of 0.05 - 50 μg kg(-1) were used to compensate the matrix effect, and reasonable recoveries 80.2 - 105.4% of five compounds were demonstrated in different spiked levels with inter-RSD from 1.7 to 10.6%. The proposed method is an alternative approach to make an analysis of neonicotinoids in Chinese medicine, which is more reliable and promising compared with other detection methods. PMID:26256607

  14. Multi-residue method for the determination of over 400 priority and emerging pollutants in water and wastewater by solid-phase extraction and liquid chromatography-time-of-flight mass spectrometry.

    PubMed

    Robles-Molina, José; Lara-Ortega, Felipe J; Gilbert-López, Bienvenida; García-Reyes, Juan F; Molina-Díaz, Antonio

    2014-07-11

    This article describes the development and validation of a liquid chromatography high-resolution mass spectrometry method for the simultaneous determination of over 400 multi-class priority and emerging pollutants with different physicochemical properties in environmental waters (surface water and wastewater). The proposed approach is based on the use of a database consisting of retention time/exact mass (of selected ions) pairs implemented with specific software for data analysis. The targeted list comprises 430 contaminants belonging to different compound categories, including 105 multiclass pharmaceuticals (analgesics/anti-inflammatories, antibiotics, lipid regulators, β-blockers, antiepileptic/psychiatrics ulcer healings, diuretics, hormones and bronchodilatadors), life-style products (caffeine, nicotine), 21 drugs of abuse and their metabolites, 279 pesticides and some of their more relevant metabolites, nitrosamines, flame retardants, plasticizers and perfluorinated compounds. The proposed approach included a simple offline solid phase extraction (SPE) step using polymeric cartridges (Oasis HLB) with 200mL of water sample loaded, followed by analysis by rapid resolution liquid chromatography electrospray time-of-flight mass spectrometry (LC-TOFMS) in both positive and negative modes. The identification of the positive findings is accomplished with the data from accurate masses of the target ions along with retention time data and characteristic in-source fragment ions. The overall method performance was satisfactory with limits of quantification lower than 10ngL(-1) for the 44% of studied compounds. Recoveries between 50% and 130% were obtained for the 65% of the analytes (281 compounds). Matrix effects occurring with wastewater matrices were also assessed. The developed method was applied to the determination of target analytes in real surface water and wastewater samples. PMID:24891157

  15. Development of an analytical method for the targeted screening and multi-residue quantification of environmental contaminants in urine by liquid chromatography coupled to high resolution mass spectrometry for evaluation of human exposures.

    PubMed

    Cortéjade, A; Kiss, A; Cren, C; Vulliet, E; Buleté, A

    2016-01-01

    The aim of this study was to develop an analytical method and contribute to the assessment of the Exposome. Thus, a targeted analysis of a wide range of contaminants in contact with humans on daily routines in urine was developed. The method focused on a list of 38 contaminants, including 12 pesticides, one metabolite of pesticide, seven veterinary drugs, five parabens, one UV filter, one plastic additive, two surfactants and nine substances found in different products present in the everyday human environment. These contaminants were analyzed by high performance liquid chromatography coupled to high resolution mass spectrometry (HPLC-HRMS) with a quadrupole-time-of-flight (QqToF) instrument from a raw urinary matrix. A validation according to the FDA guidelines was employed to evaluate the specificity, linear or quadratic curve fitting, inter- and intra-day precision, accuracy and limits of detection and quantification (LOQ). The developed analysis allows for the quantification of 23 contaminants in the urine samples, with the LOQs ranging between 4.3 ng.mL(-1) and 113.2 ng.mL(-1). This method was applied to 17 urine samples. Among the targeted contaminants, four compounds were detected in samples. One of the contaminants (tributyl phosphate) was detected below the LOQ. The three others (4-hydroxybenzoic acid, sodium dodecylbenzenesulfonate and O,O-diethyl thiophosphate potassium) were detected but did not fulfill the validation criteria for quantification. Among these four compounds, two of them were found in all samples: tributyl phosphate and the surfactant sodium dodecylbenzenesulfonate. PMID:26695319

  16. A multi-residue method for simultaneous determination of 74 pesticides in Chinese material medica using modified QuEChERS sample preparation procedure and gas chromatography tandem mass spectrometry.

    PubMed

    Liu, Xiao-qin; Li, Yun-fei; Meng, Wen-ting; Li, Dong-xiang; Sun, Henry; Tong, Ling; Sun, Guo-xiang

    2016-03-15

    The present study is focused on the development of an analytical method for the simultaneous analysis of seventy-four pesticides belonging to different chemical classes (organochlorines, organophosphates, pyrethroids, dinitroanilines, dicarboximides, triazoles, etc.) in Chinese material medica. The samples were extracted according to the acetate QuEChERS protocol. To reduce the amount of co-extracted compounds, n-hexane instead of acetonitrile was employed as the extraction solvent. To improve the overall recoveries of problematic basic and base-sensitive compounds, sodium acetate was used to adjust the pH to a neutral condition, and florisil combined with octadecyl-modified silica (C18) were utilized in the cleanup step. The samples were analysed by GC-MS/MS, and quantified by matrix-matched calibration. The validation study was carried out on two representative herbs, Chuanxiong Rhizoma and Angelica Sinensis Radix. In two matrices, the linearity of the calibration was good between 5 and 250 ng/mL concentration ranges, and the limits of quantification (LOQs) less than 0.01 mg/kg for most pesticides. At the LOQs and ten times the LOQs, the mean recoveries of almost all pesticides were within 70-120%, with relative standard deviations (RSDs) lower than 10%. The method was applied on twenty real samples. Seven batches of Chuanxiong and five batches of Danggui were found to contain the residues. The combination of modified QuEChERS and GC-MS/MS offers low cost of analysis as well as excellent accuracy and sensitivity. This method could be especially useful for trace analysis of pesticide residues in complex matrices. PMID:26894850

  17. Development of a new multi-residue laser diode thermal desorption atmospheric pressure chemical ionization tandem mass spectrometry method for the detection and quantification of pesticides and pharmaceuticals in wastewater samples.

    PubMed

    Boisvert, Michel; Fayad, Paul B; Sauvé, Sébastien

    2012-11-19

    A new solid phase extraction (SPE) method coupled to a high throughput sample analysis technique was developed for the simultaneous determination of nine selected emerging contaminants in wastewater (atrazine, desethylatrazine, 17β-estradiol, ethynylestradiol, norethindrone, caffeine, carbamazepine, diclofenac and sulfamethoxazole). We specifically included pharmaceutical compounds from multiple therapeutic classes, as well as pesticides. Sample pre-concentration and clean-up was performed using a mixed-mode SPE cartridge (Strata ABW) having both cation and anion exchange properties, followed by analysis by laser diode thermal desorption atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS). The LDTD interface is a new high-throughput sample introduction method, which reduces total analysis time to less than 15s per sample as compared to minutes with traditional liquid-chromatography coupled to tandem mass spectrometry (LC-MS/MS). Several SPE parameters were evaluated in order to optimize recovery efficiencies when extracting analytes from wastewater, such as the nature of the stationary phase, the loading flow rate, the extraction pH, the volume and composition of the washing solution and the initial sample volume. The method was successfully applied to real wastewater samples from the primary sedimentation tank of a municipal wastewater treatment plant. Recoveries of target compounds from wastewater ranged from 78% to 106%, the limit of detection ranged from 30 to 122ng L(-1) while the limit of quantification ranged from 90 to 370ng L(-1). Calibration curves in the wastewater matrix showed good linearity (R(2)≥0.991) for all target analytes and the intraday and interday coefficient of variation was below 15%, reflecting a good precision. PMID:23140957

  18. Multi-residue method for determination of 58 pesticides, pharmaceuticals and personal care products in water using solvent demulsification dispersive liquid-liquid microextraction combined with liquid chromatography-tandem mass spectrometry.

    PubMed

    Caldas, Sergiane Souza; Rombaldi, Caroline; Arias, Jean Lucas de Oliveira; Marube, Liziane Cardoso; Primel, Ednei Gilberto

    2016-01-01

    A rapid and efficient sample pretreatment using solvent-based de-emulsification dispersive liquid-liquid microextraction (SD-DLLME) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was studied for the extraction of 58 pharmaceuticals and personal care products (PPCPs) and pesticides from water samples. Type and volume of extraction and disperser solvents, pH, salt addition, amount of salt and type of demulsification solvent were evaluated. Limits of quantification (LOQ) in the range from 0.0125 to 1.25 µg L(-1) were reached, and linearity was in the range from the LOQ of each compound to 25 μg L(-1). Recoveries ranged from 60% to 120% for 84% of the compounds, with relative standard deviations lower than 29%. The proposed method demonstrated, for the first time, that sample preparation by SD-DLLME with determination by LC-MS/MS can be successfully used for the simultaneous extraction of 32 pesticides and 26 PPCPs from water samples. The entire procedure, including the extraction of 58 organic compounds from the aqueous sample solution and the breaking up of the emulsion after extraction with water, rather than with an organic solvent, was environmentally friendly. In addition, this technique was less expensive and faster than traditional techniques. Finally, the analytical method under study was successfully applied to the analysis of all 58 pesticides and PPCPs in surface water samples. PMID:26695317

  19. Analysis of pesticide multi-residues in leafy vegetables by ultrasonic solvent extraction and liquid chromatography-tandem mass spectrometry.

    PubMed

    Pan, Jian; Xia, Xiao-Xiao; Liang, Juan

    2008-01-01

    Ultrasonic solvent extraction (USE) of pesticide multi-residues including monocrotophos, dimethoate, imidacloprid, carbendazim, carbaryl and simazine from leafy vegetables is presented. The extraction procedure was optimized with regard to the solvent type and amount, sonication time and number of extraction steps. The extract did not need clean-up before injected into liquid chromatography-tandem mass spectrometry (LC-MS-MS) which was employed together with electron microscope to verify the effect of USE method. The proposed procedure allows the extraction of six pesticide residues in a single step with 40 ml of ethyl acetate for 35 min sonication, providing recovery over 83% and LOQ less than 1.4 microg/kg. The optimized USE method is a simple, low cost and an effective preparation method for determination of pesticide multi-residues at trace levels in leafy vegetables in comparison with homogenized extraction method. PMID:17664080

  20. Multi-residue fluorescent microspheres immunochromatographic assay for simultaneous determination of macrolides in raw milk.

    PubMed

    Li, Xiangmei; Shen, Jianzhong; Wang, Qi; Gao, Shuxia; Pei, Xingyao; Jiang, Haiyang; Wen, Kai

    2015-12-01

    A rapid, reliable, sensitive, and quantitative multi-residue fluorescent microspheres immunochromatographic assay (FMCA) was developed for simultaneous detection of four macrolides in raw milk. The IC50 value of the optimized FMCA was 1.36, 1.22, 1.01, and 1.39 ng/mL for erythromycin (ERY), spiramycin (SPI), tilmicosin (TIM), and tylosin (TYL), respectively. The limits of detection (LODs) for the four macrolides was 0.13 ng/mL. The recoveries of ERY, SPI, TIM, and TYL from spiked raw milk ranged from 91.8-109.2, 89.6-114.4, 84.8-111.6, and 85.8-115.2%, respectively, with coefficients of variation (CVs) of 5.4-11.3, 7.9-15.7, 6.2-13.7, and 3.2-14.9%, respectively. The whole testing process was completed within 20 min. The antibody-mixed labeled method was successfully applied to the FMCA, which greatly simplified the operation steps and saved a lot of time. Compared with the immunogold chromatographic assay (IGCA), the FMCA is more sensitive and stable and has less antibody consumption. A parallel analysis in blind raw milk samples was conducted by liquid chromatography-tandem mass spectrometry (LC-MS/MS); the results showed good correlation (r(2) = 0.99) between the two methods. Therefore, the developed multi-residue FMCA is reliable and can be easily applied to other antibiotics or other contaminants. PMID:26497839

  1. Evaluation of a method for assaying sulfonamide antimicrobial residues in cheese: hot-water extraction and liquid chromatography-tandem mass spectrometry.

    PubMed

    Berardi, Giorgio; Bogialli, Sara; Curini, Roberta; Di Corcia, Antonio; Laganá, Aldo

    2006-06-28

    Several sulfonamide antimicrobials (SAAs) are largely used in veterinary medicine. A rapid, specific, and sensitive procedure for determining 12 SAAs in cheese is presented. The method is based on the matrix solid-phase dispersion technique followed by liquid chromatography (LC)-tandem mass spectrometry (MS) equipped with an electrospray ion source. Target compounds were extracted from Mozzarella, Asiago, Parmigiano, Emmenthal, and Camembert cheese samples by 6 mL of water modified with 10% methanol and heated at 120 degrees C. The addition of methanol to hot water served to improve remarkably extraction yields of the most lipophilic SAAs, that is, sulfadimethoxine and sulfaquinoxaline. After acidification and filtration, 100 microL of the aqueous extract was injected in the LC column. MS data acquisition was performed in the multireaction monitoring mode, selecting two precursor-to-product ion transitions for each target compound. Methanol-modified hot water appeared to be an efficient extractant, because absolute recovery ranged between 67 and 88%. Using sulfamoxole as surrogate analyte, recovery of the 12 analytes spiked in the five types of cheese considered at the 50 ng/g level ranged between 75 and 105% with RSD not higher than 11%. Statistical analysis of the mean recovery data showed that the extraction efficiency was not affected by the type of cheese analyzed. This result indicates this method could be applied to other cheese types not considered here. The accuracy of the method was determined at three spike levels, that is, 20, 50, and 100 ng/g, and varied between 73 and 102% with relative standard deviations ranging between 4 and 12%. On the basis of a signal-to-noise ratio of 10, limits of quantification were estimated to be <1 ng/g. PMID:16786995

  2. A single-step pesticide extraction and clean-up multi-residue analytical method by selective pressurized liquid extraction followed by on-line solid phase extraction and ultra-high-performance liquid chromatography-tandem mass spectrometry for complex matrices.

    PubMed

    Rodrigues, Elsa Teresa; Pardal, Miguel Ângelo; Salgueiro-González, Noelia; Muniategui-Lorenzo, Soledad; Alpendurada, Maria Fátima

    2016-06-24

    Pesticides, a group of compounds linked to human activity, may, when in toxic levels, have a profound effect on water quality, and hence result in adverse consequences to aquatic life and ultimately to human health. Analytical challenges arise when successfully trying to determine these levels in environmental complex matrices. Therefore, fast, simple, sensitive and selective analytical methodologies for multi-residue determination of pesticides (atrazine, azoxystrobin, bentazon, λ-cyhalothrin, penoxsulam and terbuthylazine) in sediment, macrophytes (algae and aquatic plants) and aquatic animals were developed and validated. The established methods were matrix-dependent and were based on Selective Pressurized Liquid Extraction (SPLE) followed by on-line Solid Phase Extraction and Ultra Performance Liquid Chromatography-tandem Mass Spectrometry (on-line SPE-UPLC-ESI-MS/MS). This cutting-edge research methodology uses a small amount of sample, is time saving and reduces the use of organic solvents in compliance with Green Chemistry principles. The analytical features were adequate for all compounds in all studied matrices. The established methodology was applied on real marine samples and no pesticide concentrations above their respective method quantification limits were measured in sediments or aquatic plants. However, terbuthylazine was found in the macroalgae Ulva spp. (108ngg(-1)dw) and all the prospected pesticides were measured above their respective method quantification limits in the bivalve Scrobicularia plana (atrazine: 48ngg(-1)dw, azoxystrobin: 64ngg(-1)dw, bentazon: 33ngg(-1)dw, λ-cyhalothrin: 2531ngg(-1)dw, penoxsulam: 50ngg(-1)dw, and terbuthylazine: 44ngg(-1)dw). PMID:27234845

  3. Quinoline-2-sulfonamide

    PubMed Central

    Marciniec, Krzysztof; Maślankiewicz, Andrzej; Kusz, Joachim; Nowak, Maria

    2013-01-01

    In the title compound, C9H8N2O2S, the sulfamoyl –NH2 group is involved in inter­molecular hydrogen bonding with the sulfonamide O and quinoline N atoms. In the crystal, mol­ecules are linked into dimers via pairs of N—H⋯N hydrogen bonds, forming an R 2 2(10) motif. The dimers are further assembled into chains parallel to the b axis through N—H⋯O hydrogen bonds, generating a C(4) motif. The crystal packing is additionally stabilized by inter­molecular C—H⋯O inter­actions. The crystal studied was a non-merohedral twin with a domain ratio of 0.938 (2):0.062 (2). Density functional theory (DFT) calculations, at the B3LYP/6–31 G(d,p) level of theory, were used to optimize the mol­ecular structure and to determine inter­action energies for the title compound. The resulting inter­action energy is ∼4.4 kcal mol−1 per bridge for the C(4) chain and ∼5.9 kcal mol−1 per bridge for the R 2 2(10) motif. PMID:24109421

  4. Multi-class, multi-residue analysis of trace veterinary drugs in milk by rapid screening and quantification using ultra-performance liquid chromatography-quadrupole time-of-flight mass spectrometry.

    PubMed

    Zhang, Yaqian; Li, Xiang; Liu, Xiaomao; Zhang, Jinjie; Cao, Yanzhong; Shi, Zhihong; Sun, Hanwen

    2015-12-01

    A simple and rapid multi-class multi-residue analytical method was developed for the screening and quantification of veterinary drugs in milk by ultra-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS). A total of 90 veterinary drugs investigated belonged to almost 20 classes including lincomycins, macrolides, sulfonamides, quinolones, tetracyclines, β-agonists, β-lactams, sedatives, β-receptor antagonists, sex hormones, glucocorticoids, nitroimidazoles, benzimidazoles, nitrofurans, and some others. A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure was developed for the sample preparation without the solid-phase extraction step. The linearity, sensitivity, accuracy, repeatability, and reproducibility of the method were fully validated. The response of the detector was linear for each target compound in a wide concentration range with a correlation coefficient (R(2)) of 0.9973 to 0.9999 (among them R(2)>0.999 for 73 of 90 analytes). The range of the limit of quantification for these compounds in the milk ranged from 0.10 to 17.30μg/kg. The repeatability and reproducibility were in the range of 2.11 to 9.62% and 2.76 to 13.9%, respectively. The average recoveries ranged from 72.62 to 122.2% with the RSD (n=6) of 1.30 to 9.61% at 3 concentration levels. For the screening method, the data of the precursor and product ions of the target analytes were simultaneously acquired under the all ions MS/MS mode in a single run. An accurate mass database for the confirmation and identification of the target compounds was established. The applicability of the screening method was verified by applying to real milk samples. The proposed analytical method allows the identification and confirmation of the target veterinary drugs at trace levels employing quick analysis time. Certain veterinary drugs were detected in some cases. PMID:26506545

  5. Determination of Sulfonamide Residues in Food by Micellar Liquid Chromatography

    PubMed Central

    Szymański, Arkadiusz

    2008-01-01

    This paper presents new methods of determination of sulfonamide residues in food products of animal origin, based on liquid chromatography with a micellar mobile phase. The methods employ a technique of direct injection of the sample and preliminary isolation of the analyte by extraction in the liquid-solid and liquid-liquid system. The methods have been characterized by providing the parameters of the calibration curves, the range of linearity, limit of detection, and precision and accuracy of particular determinations. The recovery of the sulfonamides introduced into the food products studied has also been determined. PMID:19696937

  6. Multi-class, multi-residue analysis of pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenyl ethers and novel flame retardants....mass spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A multi-class, multi-residue method for the analysis of 13 novel flame retardants, 18 representative pesticides, 14 polychlorinated biphenyl (PCB) congeners, 16 polycyclic aromatic hydrocarbons (PAHs), and 7 polybrominated diphenyl ether (PBDE) congeners in catfish muscle was developed and evaluated...

  7. Quantitative determination of sulfonamide residues in foods of animal origin by high-performance liquid chromatography with fluorescence detection.

    PubMed

    Stoev, G; Michailova, A

    2000-02-25

    An HPLC method with fluorescence detection is proposed for the quantitative determination of residues of ten of the most used sulfonamides as their derivatives. Sulfonamides were isolated from meat, mix meat and kidney with ethyl acetate (first extraction) and acetone (second extraction) and further purified by partitioning three times with water-methylene chloride. The recovery for mix meat spiked with 1, 5 and 10 microg/kg of sulfonamides averaged 64%, 68% and 75%, respectively. Limits of quantitation were 1 microg/kg for sulfaquinoxaline and 0.5 microg/kg for the remaining sulfonamides. PMID:10735284

  8. 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

  9. Synthesis of new sulfonamides as lipoxygenase inhibitors.

    PubMed

    Mustafa, Ghulam; Khan, Islam Ullah; Ashraf, Muhammad; Afzal, Iftikhar; Shahzad, Sohail Anjum; Shafiq, Muhammad

    2012-04-15

    The present study describes a convenient method for the synthesis of new lipoxygenase inhibitors, 4-(toluene-4-sulfonylamino)-benzoic acids from p-amino benzoic acid. Reaction of p-amino benzoic acid with p-toluenesulfonyl chloride provided thirteen N- and O-alkylation products 4a-4m in moderate to good yields. Lipoxygenase inhibition of newly formed sulfonamide derivatives was investigated and some of these compounds 4m, 4g, 4e, 4f and 4j showed good lipoxygenase inhibitory activities with IC(50) values ranged between 15.8 ± 0.57 and 91.7 ± 0.61 μmol whilst all other compounds exhibited mild anti-lipoxygenase activities with IC(50) values ranged between 139.2 ± 0.75 and 232.1 ± 0.78 μmol. N-alkylated products were more active against the enzyme than O-alkylated or both N- and O-alkylated ones. All synthesized sulfonamides were recrystallized in chloroform to give these title compounds which were characterized using FTIR, (1)H NMR, (13)C NMR, elemental analysis and single crystal X-ray diffraction techniques. PMID:22436389

  10. [The discovery of hypoglycemic sulfonamides].

    PubMed

    Loubatières-Mariani, Marie-Madeleine

    2007-01-01

    In 1933 Auguste Loubatières started to work at the Physiological Laboratory of the Montpellier Medical School, famous for the scientific work of Emmanuel Hédon and then Louis Hédon on experimental diabetes mellitus. Auguste Loubatières was particularly interested in the study of a new preparation of long-lasting insulin (insulin-protamine-zinc: IPZ) in the totally pancreatectomized dog. In 1938, he observed that high doses of IPZ induced a severe and protracted hypoglycemia entailing convulsive attacks and even irreversible coma. The story of hypoglycemic sulfonamides started in France in spring 1942. During the second world war, because of the food shortage in Montpellier, a lot of people ate rotting food or even food contaminated with bacteria, such as shellfish. Many cases of thyphoid fever were diagnosed and treated by Marcel Janbon at the Clinic of the Montpellier Medical School with a new sulfonamide (VK 57 or 2254 RP). Adverse reactions were observed: in some patients, convulsions and even prolonged coma occurred; in some others a major drop in blood glucose was observed. M. Janbon informed the physiologists about these observations questioning them for an interpretation. A. Loubatières was particularly interested and immediately undertook animal trials. On June 13, 1942, he observed that repeated oral administration of 2254 RP in the normal fasting conscious dog induced a progressive, marked and long-lasting decrease in glycemia. He continued his experiments and definitively established the hypoglycemic effect of this sulfonamide. However the mechanism of action remained to be established. The pattern of some graphs reminded him that of some others he could previously observe in the study with IPZ; it occurred to him that 2254 RP could lower the blood glucose concentration by stimulating insulin secretion. He had then to establish the validity of his hypothesis. From 1942 to 1946, A. Loubatières performed a systematic study of the effects of 2254 RP

  11. Synthesis of Heteroaryl Sulfonamides from Organozinc Reagents and 2,4,6-Trichlorophenyl Chlorosulfate

    PubMed Central

    2016-01-01

    A method for the preparation of aryl and heteroaryl sulfonamides using 2,4,6-trichlorophenyl chlorosulfate (TCPC) is described. The reaction of 2-pyridylzinc reagents with TCPC resulted in 2,4,6-trichlorophenyl (TCP) pyridine-2-sulfonates, and the parent pyridine-2-sulfonate was shown to react with amines. Less electron-rich aryl- and heteroarylzinc reagents reacted with TCPC to afford sulfonyl chlorides that were converted in situ to sulfonamides. PMID:26065317

  12. A generic and rapid strategy for determining trace multiresidues of sulfonamides in aquatic products by using an improved QuEChERS method and liquid chromatography-electrospray quadrupole tandem mass spectrometry.

    PubMed

    Kung, Te-An; Tsai, Chung-Wei; Ku, Bing Chang; Wang, Wei-Hsien

    2015-05-15

    A rapid and efficient multiresidue method that involves using improved QuEChERS method and liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS/MS) was developed to measure trace levels of sulfonamides in fish tissue. This proposed method was proven to be a powerful, highly sensitive, and environmentally friendly analytical tool that requires minimal sample preparation. The typical MS/MS fragmentation patterns of the [M+H](+) were 156 m/z, 108 m/z, and 92 m/z. Separation was performed on HC-C18 columns with a gradient elution by using methanol -5mM ammonium acetate containing formic acid (pH 3.5). This method was validated and exhibited favorable performance as well as acceptable accuracy (80.2-93.5%), precision (3.82-8.71%), sensitivity (limits of detection (LODs) 0.43-1.22 μg kg(-1), limits of quantification (LOQs) 1.27-3.71 μg kg(-1); decision limit (CCα) 1.49-10.9 μg kg(-1), detection capability (CCβ) 1.71-11.4 μg kg(-1)), and an acceptable matrix effect (-18.2-18.4%). This methodology has been successfully applied in analyzing various fish tissue from local markets. PMID:25577069

  13. Evaluation of Polymorphisms in the Sulfonamide Detoxification Genes CYB5A and CYB5R3 in Dogs with Sulfonamide Hypersensitivity

    PubMed Central

    Funk-Keenan, J.; Sacco, J.; (Amos) Wong, Y. Y.; Rasmussen, S.; Motsinger-Reif, A.; Trepanier, L. A.

    2015-01-01

    Background Delayed hypersensitivity (HS) reactions to potentiated sulfonamide antimicrobials occur in both dogs and humans, and involve an intermediate hydroxylamine metabolite that is detoxified by cytochrome b5 and NADH cytochrome b5 reductase. Hypothesis/Objectives We hypothesized that polymorphisms in the genes (CYB5A and CYB5R3) encoding these 2 enzymes would be associated with risk of sulfonamide HS in dogs. Animals A total of 18 dogs with delayed HS to potentiated sulfonamide antimicrobials and 16 dogs that tolerated (TOL) a therapeutic course of these drugs without adverse effect. Methods CYB5A and CYB5R3 were sequenced from canine liver, and the promoter, exons, and 3′ untranslated regions of both genes were resequenced from genomic DNA obtained from all dogs. Results Multiple polymorphisms were found in both genes. When controlled for multiple comparisons, the 729GG variant in CYB5R3 was significantly overrepresented in dogs with sulfonamide HS (78% of dogs), compared to TOL dogs (31%; P = .003). Conclusions and Clinical Importance The CYB5R3 729GG variant may contribute to the risk of sulfonamide HS in dogs. Functional characterization of this polymorphism, as well as genotyping in a larger number of HS and TOL dogs, is warranted. PMID:22816446

  14. Multi-residue determination of polyhalogenated carbazoles in aquatic sediments.

    PubMed

    Wu, Yan; Moore, Jeremy; Guo, Jiehong; Li, An; Grasman, Keith; Choy, Steven; Chen, Da

    2016-02-19

    Recent studies have discovered a number of polyhalogenated carbazoles (PHCZs) in aquatic sediments and soil. These substances are attracting emerging concern due to their environmental presence, persistence, and potential dioxin-like activities. In response to the increasing interests in these chemicals, the present study aimed to develop an efficient and sensitive analytical methodology for quantitative determination of environmentally relevant PHCZs in aquatic sediments. The developed method employed time- and solvent-saving extraction and cleanup procedures and utilized gas chromatogram-mass spectrometry (GC-MS) for separation and determination of PHCZ analytes. PHCZs substituted with bromine atom(s) (except for 3-bromocarbazole) or a combination of bromine and chlorine atoms were analyzed by GC-MS in the electron-capture negative ionization (ECNI) mode, whereas congeners substituted with chlorine atoms as well as 3-bromocarbazole were analyzed in electron impact (EI) ionization mode. The developed method demonstrated negligible matrix effects, satisfactory and stable recoveries, and low method limits of quantification (0.11-0.53 ng/g dry weight (dw)) of target analytes. Using this method, we successfully determined a number of PHCZs in surface sediments from the Saginaw River system (Michigan, USA) and the Saginaw Bay of Lake Huron, with the summed concentrations of PHCZ congeners ranging up to 46.3 ng/g dw. Given that further investigations are needed to better elucidate the sources, environmental behavior, fate, and toxicity of PHCZs, highly sensitive and efficient analytical methodologies would be essentially needed to fill in these knowledge gaps. PMID:26818240

  15. Ecotoxicity evaluation of selected sulfonamides.

    PubMed

    Białk-Bielińska, Anna; Stolte, Stefan; Arning, Jürgen; Uebers, Ute; Böschen, Andrea; Stepnowski, Piotr; Matzke, Marianne

    2011-10-01

    Sulfonamides (SAs) are a group of antibiotic drugs widely used in veterinary medicine. The contamination of the environment by these pharmaceuticals has raised concern in recent years. However, knowledge of their (eco)toxicity is still very basic and is restricted to just a few of these substances. Even though their toxicological analysis has been thoroughly performed and ecotoxicological data are available in the literature, a systematic analysis of their ecotoxicological potential has yet to be carried out. To fill this gap, 12 different SAs were chosen for detailed analysis with the focus on different bacteria as well as non-target organisms (algae and plants). A flexible (eco)toxicological test battery was used, including enzymes (acetylcholinesterase and glutathione reductase), luminescent marine bacteria (Vibrio fischeri), soil bacteria (Arthrobacter globiformis), limnic unicellular green algae (Scenedesmus vacuolatus) and duckweed (Lemna minor), in order to take into account both the aquatic and terrestrial compartments of the environment, as well as different trophic levels. It was found that SAs are not only toxic towards green algae (EC₅₀=1.54-32.25 mg L⁻¹) but have even stronger adverse effect on duckweed (EC₅₀=0.02-4.89 mg L⁻¹) than atrazine - herbicide (EC₅₀=2.59 mg L⁻¹). PMID:21752420

  16. Determination of 10 sulfonamide residues in meat samples by liquid chromatography with ultraviolet detection.

    PubMed

    Di Sabatino, Marcello; Di Pietra, Anna Maria; Benfenati, Luigi; Di Simone, Bruno

    2007-01-01

    A liquid chromatography (LC) method is described for the simultaneous determination of 10 commonly used sulfonamide drug residues in meat. The 10 sulfonamide drugs of interest were sulfadiazine, sulfathiazole, sulfamerazine, sulfadimidine, sulfamethizole, sulfamonomethoxine, sulfachloropyridazine, sulfadoxine, sulfadimethoxine, and sulfaquinoxaline. The residues were extracted with acetone-chloroform (1 + 1). Sulfonamides were quantitatively retained in the extracting solution and afterwards eluted from a cation-exchanger solid-phase extraction cartridge with a solution of methanol-aqueous ammonia. The solution was dried, reconstituted with 5 mL methanol and filtered before analysis by LC-ultraviolet using a C18 column with a mobile phase gradient of potassium dihydrogen phosphate buffer, pH 2.5, and methanol-acetonitrile (30 + 70, v/v). The method was applied to cattle, swine, chicken, and sheep muscle tissues. The validation was performed with a fortified cattle meat sample at level of 100 ppb, which is the administrative maximum residue limit for sulfonamides in the European Union. The limit of quantitation for all sulfonamides was between 3 and 14 ppb. Recovery was evaluated for different meat matrixes. The mean recovery values were between 66.3% for pork meat samples and 71.5% for cattle meat samples. PMID:17474530

  17. 40 CFR 721.9570 - Halophenyl sulfonamide salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halophenyl sulfonamide salt. 721.9570... Substances § 721.9570 Halophenyl sulfonamide salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halophenyl sulfonamide salt (PMN...

  18. 40 CFR 721.9570 - Halophenyl sulfonamide salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halophenyl sulfonamide salt. 721.9570... Substances § 721.9570 Halophenyl sulfonamide salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halophenyl sulfonamide salt (PMN...

  19. 40 CFR 721.9570 - Halophenyl sulfonamide salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halophenyl sulfonamide salt. 721.9570... Substances § 721.9570 Halophenyl sulfonamide salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halophenyl sulfonamide salt (PMN...

  20. 40 CFR 721.9570 - Halophenyl sulfonamide salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halophenyl sulfonamide salt. 721.9570... Substances § 721.9570 Halophenyl sulfonamide salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halophenyl sulfonamide salt (PMN...

  1. 40 CFR 721.9570 - Halophenyl sulfonamide salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halophenyl sulfonamide salt. 721.9570... Substances § 721.9570 Halophenyl sulfonamide salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halophenyl sulfonamide salt (PMN...

  2. Multi-residue determination of pesticides in tropical fruits using liquid chromatography/tandem mass spectrometry.

    PubMed

    Botero-Coy, A M; Marín, J M; Ibáñez, M; Sancho, J V; Hernández, F

    2012-03-01

    Monitoring pesticide residues in tropical fruits is of great interest for many countries, e.g., from South America, that base an important part of their economy on the exportation of these products. In this work, a LC-MS/MS multi-residue method using a triple quadrupole analyzer has been developed for around 30 pesticides in seven Colombian tropical fruits of high commercial value for domestic and international markets (uchuva, tamarillo, granadilla, gulupa, maracuya, papaya, and pithaya). After sample extraction with acetonitrile, an aliquot of the extract was diluted with water and directly injected into the HPLC-MS/MS system (electrospray interface) without any cleanup step. The formation of sodium adducts-of poor fragmentation-was minimized using 0.1% formic acid in the mobile phase, which favored the formation of the protonated molecule. However, the addition of ammonium acetate made the formation of the ammonium adducts in some particular cases possible, avoiding the presence of the sodium adducts. The highest sensitivity was observed in positive electrospray ionization for the wide majority of pesticides, with a few exceptions for acidic compounds that gave better response in the negative mode (e.g., 2,4-D, fluazinan). Thus, simultaneous acquisition on the positive/negative mode was applied. Two MS/MS transitions were acquired for each compound to ensure a reliable quantification and identification of the compounds detected in samples, although for malathion a third transition was acquired due to the presence of interfering isobaric compounds in the sample extracts. A detailed study of matrix effects was made by a comparison of standards in solvent and in matrix. Both ionization suppression and ionization enhancement were observed depending on the analyte/matrix combination tested. Correction of matrix effects was made by the application of calibration in matrix. Three matrices were selected (uchuva, maracuya, gulupa) to perform matrix calibration in the

  3. Multi-residue analysis of organic pollutants in hair and urine for matrices comparison.

    PubMed

    Hardy, Emilie M; Duca, Radu C; Salquebre, Guillaume; Appenzeller, Brice M R

    2015-04-01

    Urine being currently the most classically used matrix for the assessment of human exposure to pesticides, a growing interest is yet observed in hair analysis for the detection of organic pollutants. The aim of the present work was to develop and to validate multi-residue analytical methods, as similar as possible, in order to determine pesticides and their metabolites in these two biological matrices despite their different nature. The list of parent compounds and their metabolites investigated here consisted of 56 compounds, including organochlorines, organophosphates, pyrethroids, carbamates, other pesticides and polychlorinated biphenyls (PCBs). Two different approaches were necessary for the analysis of non-polar compounds (mainly parents) on one hand and polar analytes (mainly metabolites) on the other hand. In the final procedure, extraction from hair was carried out with acetonitrile/water after sample decontamination and pulverization. Extract was split into two fractions, which were analyzed directly with solid phase microextraction (SPME) injection for non-polar compounds and after derivatization with liquid injection for polar compounds. In urine, non-polar compounds were analyzed directly using SPME. Polar compounds were analyzed after acidic hydrolysis, liquid-liquid extraction with acetonitrile-cyclohexane-ethyl acetate, derivatization and liquid injection. Analysis was performed with gas chromatography tandem mass spectrometry operating in negative chemical ionization (GC-MS/MS-NCI) for all the compounds (non-polar and polar) in the two matrices. In hair, limits of quantification (LOQ) ranged from 0.02 pg/mg for trifluralin to 5.5 pg/mg for diethylphosphate. In urine, LOQ ranged from 0.4 pg/mL for α-endosulfan to 4 ng/mL for dimethyldithiophosphate. The analysis of samples supplemented with standards and samples collected from an animal previously submitted to chronic exposure to pesticides confirmed that all the compounds were analyzable in both

  4. Trace determination of sulfonamides residues in meat with a combination of solid-phase microextraction and liquid chromatography-mass spectrometry.

    PubMed

    Lu, Kuan-Hui; Chen, Chung-Yu; Lee, Maw-Rong

    2007-05-15

    An integrated method of combining solid-phase microextraction (SPME) with liquid chromatography-mass spectrometry (LC-MS) was evaluated for determination trace amount of sulfonamides in meat products. Eight commonly used sulfonamides, sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMT), sulfamonomethoxine (SMMX), sulfamethoxazole (SMXZ), sulfaquinoxaline (SQX) and sulfadimethoxine (SDMX), were investigated in this study. Chromatography was performed on a C(18) reversed-phase column using an isocratic acetonitrile in water as the mobile phase. Fiber coated with a 65mum thickness of polydimethylsiloxane/divinylbenzene (PDMS/DVB) was used to extract sulfonamides at optimum conditions. Analytes were desorbed with static desorption in an SPME-HPLC desorbed chamber for 15min and then determined by LC-MS. The detection limits of these sulfonamides in pork were from 16mugkg(-1) (SMT) to 39mugkg(-1) (SMMX). According to the analysis, the linear range was from 50 to 2000mugkg(-1) with relative standard deviation (R.S.D.s) value below 15% (intra-day) and 19% (inter-day). The proposed method was tested by analyzing meats from a local market for sulfonamides residues. Some sulfonamides in our study were detected in the meat samples. The concentration of these residual sulfonamides ranged from 66mugkg(-1) (SDZ) to 157mugkg(-1) (SQX) in a chicken sample. The results demonstrate that the SPME-LC-MS system is highly effective in analyzing trace sulfonamides in meat products. PMID:19071729

  5. Iridium(iii)-catalyzed regioselective C7-sulfonamidation of indoles.

    PubMed

    Song, Zengqiang; Antonchick, Andrey P

    2016-06-01

    Iridium(iii)-catalyzed direct C7-sulfonamidation of indoles with sulfonyl azides is described. The developed method has good compatibility with diverse functional groups, providing various 7-amino-substituted indoles with good to excellent yields in a short time under mild reaction conditions. The key feature of the developed method is the regioselective functionalization at the C7-position of 2,3-unsubstituted indoles. Biologically active compounds can be obtained using this protocol. The application of the iridium(iii) catalyst and directing group plays a crucial role in the regioselectivity of the developed reaction. PMID:27173668

  6. Nucleophilic addition of sulfonamides to bromoacetylenes: facile preparation of pyrroles.

    PubMed

    Yamagishi, Masahito; Nishigai, Ken; Hata, Takeshi; Urabe, Hirokazu

    2011-09-16

    Nucleophilic addition of sulfonamides to 1-bromo-1-alkynes provided (Z)-N-(1-bromo-1-alken-2-yl)-p-toluenesulfonamides in good yield and in a highly regio- and stereoselective manner. Treatment of product (Z)-N-(1-bromo-1-octen-2-yl)-N-allyl-p-toluenesulfonamide with a palladium catalyst under Heck conditions afforded 1-(p-toluenesulfonyl)-2-hexyl-4-methylpyrrole in good yield. Other pyrroles with various substituents can also be prepared in good yield by this method. PMID:21842873

  7. A simple urine test for sulfonamides

    PubMed Central

    de Almeida-Filho, Juvenal; de Souza, José Maria

    1983-01-01

    The lack of a simple and reliable test for sulfonamides has created a problem because of the increasing use of these drugs in the chemotherapy of malaria. This paper describes a modification of the Bratton-Marshall technique, for which the reagents are easily obtainable and which can be carried out in simply equipped primary health care laboratories. PMID:6601540

  8. Evaluation of polymorphisms in the sulfonamide detoxification genes NAT2, CYB5A, and CYB5R3 in patients with sulfonamide hypersensitivity

    PubMed Central

    Sacco, James; Abouraya, Mahmoud; Motsinger-Reif, Alison; Yale, Steven; McCarty, Catherine; Trepanier, Lauren

    2013-01-01

    Objective To determine whether polymorphisms in the sulfonamide detoxification genes, CYB5A (encoding cytochrome b5), CYB5R3 (encoding cytochrome b5 reductase), or NAT2 (encoding N-acetyltransferase 2) were over-represented in patients with delayed sulfonamide drug hypersensitivity, compared to control patients that tolerated a therapeutic course of trimethoprim-sulfamethoxazole without adverse event. Methods DNA from 99 non-immunocompromised patients with sulfonamide hypersensitivity that were identified from the Personalized Medicine Research Project at the Marshfield Clinic, and from 99 age-, race-, and gender-matched drug-tolerant controls, were genotyped for four CYB5A and five CYB5R3 polymorphisms, and for all coding NAT2 SNPs. Results CYB5A and CYB5R3 SNPs were found at low allele frequencies (less than 3–4%), which did not differ between hypersensitive and tolerant patients. NAT2 allele and haplotype frequencies, as well as inferred NAT2 phenotypes, also did not differ between groups (60% vs. 59% slow acetylators). Finally, no difference in NAT2 status was found in a subset of patients with more severe hypersensitivity signs (drug reaction with eosinophilia and systemic symptoms; DRESS) compared to tolerant patients. Conclusions We found no evidence for a substantial involvement of these 9 CYB5A or CYB5R3 polymorphisms in sulfonamide HS risk, although minor effects cannot be completely ruled out. Despite careful medical record review and full re-sequencing of the NAT2 coding region, we found no association of NAT2 coding alleles with sulfonamide hypersensitivity (predominantly cutaneous eruptions) in this adult Caucasian population. PMID:22850190

  9. Monoclonal antibodies with group specificity toward sulfonamides: Selection of hapten and antibody selectivity

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Although many antibodies to sulfonamides have been generated, immunoassays based on the current available antibodies for large multi-sulfonamide screening programs have properties dependent on the immunizing hapten structure and have always suffered from high selectivity for individual sulfonamides....

  10. Rapid and sensitive determination of sulfonamide residues in milk and chicken muscle by microfluidic chip electrophoresis.

    PubMed

    Wang, Lili; Wu, Jing; Wang, Qin; He, Chonghui; Zhou, Lei; Wang, Jing; Pu, Qiaosheng

    2012-02-22

    A new, rapid, and sensitive method was proposed for the determination of sulfonamide residues in milk and chicken muscle samples by microchip electrophoresis with laser-induced fluorescence detection. Separation of fluorescamine-labeled sulfonamides was accomplished by using a buffer containing 5 mmol/L boric acid and 1% (w/v) polyvinyl alcohol (PVA). The pH, amount of PVA, and concentration of boric acid in the running buffer were found to have great influence on the separation. By optimizing these conditions, the separation of four sulfonamides, sulfamethazine, sulfamethoxazole, sulfaquinoxaline, and sulfanilamide, was achieved within 1 min with limits of detection (S/N = 3) of 0.2-2.3 μg/L, which are well below the maximum residue limit. The proposed method also exhibited very good repeatability; the relative standard deviations for both within-day and between-day measurements were ≤3.0%. With a simplified sample pretreatment protocol, fast determination of sulfonamides in real samples was successfully performed with standard addition recoveries of 93.3-100.8 and 82.9-92.3%, respectively. PMID:22277081

  11. Genome-Wide Association Study in Immunocompetent Patients with Delayed Hypersensitivity to Sulfonamide Antimicrobials

    PubMed Central

    Motsinger-Reif, Alison; Dickey, Allison; Yale, Steven; Trepanier, Lauren A.

    2016-01-01

    Background Hypersensitivity (HS) reactions to sulfonamide antibiotics occur uncommonly, but with potentially severe clinical manifestations. A familial predisposition to sulfonamide HS is suspected, but robust predictive genetic risk factors have yet to be identified. Strongly linked genetic polymorphisms have been used clinically as screening tests for other HS reactions prior to administration of high-risk drugs. Objective The purpose of this study was to evaluate for genetic risk of sulfonamide HS in the immunocompetent population using genome-wide association. Methods Ninety-one patients with symptoms after trimethoprim-sulfamethoxazole (TMP-SMX) attributable to “probable” drug HS based on medical record review and the Naranjo Adverse Drug Reaction Probability Scale, and 184 age- and sex-matched patients who tolerated a therapeutic course of TMP-SMX, were included in a genome-wide association study using both common and rare variant techniques. Additionally, two subgroups of HS patients with a more refined clinical phenotype (fever and rash; or fever, rash and eosinophilia) were evaluated separately. Results For the full dataset, no single nucleotide polymorphisms were suggestive of or reached genome-wide significance in the common variant analysis, nor was any genetic locus significant in the rare variant analysis. A single, possible gene locus association (COL12A1) was identified in the rare variant analysis for patients with both fever and rash, but the sample size was very small in this subgroup (n = 16), and this may be a false positive finding. No other significant associations were found for the subgroups. Conclusions No convincing genetic risk factors for sulfonamide HS were identified in this population. These negative findings may be due to challenges in accurately confirming the phenotype in exanthematous drug eruptions, or to unidentified gene-environment interactions influencing sulfonamide HS. PMID:27272151

  12. Synthesis and antibacterial activity of sulfonamides. SAR and DFT studies

    NASA Astrophysics Data System (ADS)

    Boufas, Wahida; Dupont, Nathalie; Berredjem, Malika; Berrezag, Kamel; Becheker, Imène; Berredjem, Hajira; Aouf, Nour-Eddine

    2014-09-01

    A series of substituted sulfonamide derivatives were synthesized from chlorosulfonyl isocyanate (CSI) in tree steps (carbamoylation, sulfamoylation and deprotection). Antibacterial activity in vitro of some newly formed compounds investigated against clinical strains Gram-positive and Gram-negative: Escherichia coli and Staphylococcus aureus applying the method of dilution and minimal inhibition concentration (MIC) methods. These compounds have significant bacteriostatic activity with totalities of bacterial strains used. DFT calculations with B3LYP/6-31G(d) level have been used to analyze the electronic and geometric characteristics deduced for the stable structure of three compounds presenting conjugation between a nitrogen atom N through its lone pair and an aromatic ring next to it. The principal quantum chemical descriptors have been correlated with the antibacterial activity.

  13. Multi-residue pesticide analysis (gas chromatography-tandem mass spectrometry detection)-Improvement of the quick, easy, cheap, effective, rugged, and safe method for dried fruits and fat-rich cereals-Benefit and limit of a standardized apple purée calibration (screening).

    PubMed

    Rasche, Claudia; Fournes, Britta; Dirks, Uwe; Speer, Karl

    2015-07-17

    Some steps of the QuEChERS method for the analysis of pesticides with GC-MS/MS in cereals and dried fruits were improved or simplified. For the latter, a mixing vessel with stator-rotor-system proved to be advantageous. The extraction procedure of dried fruits is much easier and safer than the Ultra Turrax and results in excellent validation data at a concentration level of 0.01mg/kg (116 of 118 analytes with recoveries in the range of 70-120%, 117 of 118 analytes with RSD <20%). After qualifying problematic lipophilic pesticides in fat-rich cereals (fat content >7%), predominantly organochlorines showed recoveries of <70% in quantification when the standard QuEChERS method with water was used. A second extraction was carried out analogous to the QuEChERS method, however, without the addition of water. With this simple modification, the problematic lipophilic pesticides, which had been strongly affected by the fat content of the commodities, could be determined with recoveries above 70% even at a concentration level of 0.01mg/kg. Moreover, a GC-MS/MS screening method for 120 pesticides at a concentration level of 0.01mg/kg was established by employing analyte protectants (ethylglycerol, gulonolactone, and sorbitol). The use of only one standardized calibration, made of an apple purée extract in combination with analyte protectants, allowed for a qualitative and quantitative analysis of 120 pesticides in different matrix extracts (tomato, red pepper, sour cherries, dried apples, black currant powder, raisins, wheat flour, rolled oats, wheat germ). The analyte protectants leveled the differences in the matrix-induced protection effect of the analyzed extracts over a wide range. The majority of the pesticides were analyzed with good analytical results (recoveries in the range of 70-120% and RSD <20%). PMID:26044382

  14. Thermodynamic and structural aspects of sulfonamide crystals and solutions.

    PubMed

    Perlovich, German L; Tkachev, Valery V; Strakhova, Nadezda N; Kazachenko, Vladimir P; Volkova, Tatyana V; Surov, Oleg V; Schaper, Klaus-Jürgen; Raevsky, Oleg A

    2009-12-01

    The crystal structures of three sulfonamides with the general structure 4-NH(2)-C(6)H(4)-SO(2)NH-C(6)H(4/3)-R (R = 4-Et; 4-OMe; 5-Cl-2-Me) have been determined by X-ray diffraction. On the basis of our previous data and the results obtained a comparative analysis of crystal properties was performed: molecular conformational states, packing architecture, and hydrogen bond networks using graph set notations. The thermodynamic aspects of the sulfonamide sublimation process have been studied by investigating the temperature dependence of vapor pressure using the transpiration method. A regression equation was derived describing the correlation between sublimation entropy terms and crystal density data calculated from X-ray diffraction results. Also correlations between sublimation Gibbs energies and melting points, on the one hand, and between sublimation enthalpies and fusion enthalpies at 298 K, on the other hand, were found. These dependencies give the opportunity to predict sublimation thermodynamic parameters by simple thermo-physical experiments (fusion characteristics). Solubility processes of the compounds in water, n-hexane, and n-octanol (as phases modeling various drug delivery pathways and different types of membranes) were investigated and corresponding thermodynamic functions were calculated as well. Thermodynamic characteristics of sulfonamide solvation were evaluated. For compounds with similar structures processes of transfer from one solvent to another one were studied by a diagram method combined with analysis of enthalpic and entropic terms. Distinguishing between enthalpy and entropy, as is possible through the present approach, leads to the insight that the contribution of these terms is different for different molecules (entropy- or enthalpy-determined). Thus, in contrast to interpretation of only the Gibbs energy of transfer, being extensively used for pharmaceuticals in the form of the partition coefficient (log P), the analysis of

  15. Determination of sulfonamide residues in eggs by liquid chromatography.

    PubMed

    Furusawa, Naoto

    2002-01-01

    A method was developed for determining residual sulfonamide antibacterials such as sulfamethazine (SMZ), sulfamonomethoxine (SMM), sulfadimethoxine (SDM), and sulfaquinoxaline (SQ) in eggs using liquid chromatography with a photodiode array detector. The spiked and blank samples were cleaned up by using an Ultrafree-MC/PL centrifugal ultrafiltration unit. A Mightysil RP-4 GP column and a mobile phase of 28% (v/v) ethanol-H2O with a photodiode array detector were used for the determination. Average recoveries from eggs spiked with each drug at 0.1, 0.2, 0.4, and 1.0 ppm were > or = 80.9%, with relative standard deviations between 1.3 and 4.7%. The limits of quantitation were 0.060 ppm for SMZ, 0.045 for SMM, 0.044 for SDM, and 0.093 for SQ. The analysis of one sample required < 30 min and < 5 mL ethanol as solvent. PMID:12180677

  16. Development, validation, and uncertainty measurement of multi-residue analysis of organochlorine and organophosphorus pesticides using pressurized liquid extraction and dispersive-SPE techniques.

    PubMed

    Sanyal, Doyeli; Rani, Anita; Alam, Samsul; Gujral, Seema; Gupta, Ruchi

    2011-11-01

    Simple and efficient multi-residue analytical methods were developed and validated for the determination of 13 organochlorine and 17 organophosphorous pesticides from soil, spinach and eggplant. Techniques namely accelerated solvent extraction and dispersive SPE were used for sample preparations. The recovery studies were carried out by spiking the samples at three concentration levels (1 limit of quantification (LOQ), 5 LOQ, and 10 LOQ). The methods were subjected to a thorough validation procedure. The mean recovery for soil, spinach and eggplant were in the range of 70-120% with median CV (%) below 10%. The total uncertainty was evaluated taking four main independent sources viz., weighing, purity of the standard, GC calibration curve and repeatability under consideration. The expanded uncertainty was well below 10% for most of the pesticides and the rest fell in the range of 10-20%. PMID:21210211

  17. Rapid separation and highly sensitive detection methodology for sulfonamides in shrimp using a monolithic column coupled with BDD amperometric detection.

    PubMed

    Sangjarusvichai, Haruthai; Dungchai, Wijitar; Siangproh, Weena; Chailapakul, Orawon

    2009-09-15

    In this report, we aimed to extend our previous efforts toward the evaluation of sulfonamides (SAs) with a boron-doped diamond (BDD) electrode. We improved this method by reducing the analysis time using a monolithic column coupled with amperometric detection to determine seven sulfonamides (sulfaguanidine, sulfadiazine, sulfamethazine, sulfamonomethoxine, sulfamethoxazole, sulfadimethoxine and sulfaquinoxaline). Because of its rapid separation, low back-pressure and high separation efficiency compared to a particle-packed column, a monolithic column (100 mm x 4.6mm) was used for sulfonamide separation. Chromatographic separation was performed in less than 8 min. The analysis was carried out using phosphate buffer (0.1M, pH 3): acetonitrile: methanol in a ratio of 80:15:5 (v/v/v) as the mobile phase with a flow rate of 1.5 mL min(-1). The optimal detection potential using hydrodynamic voltammetry was found to be 1.2V versus Ag/AgCl. The method was applied to determine seven sulfonamides in shrimp after sample preparation by solid-phase extraction. The recoveries of the sulfonamides in spiked shrimp samples at 1.5, 5 and 10 microg g(-1) were in the range of 81.7 to 97.5% with a relative standard deviation (R.S.D.) between 1.0 and 4.6%. Our methodology produced results that were highly correlated with HPLC-MS data. Therefore, we propose a method that can be used for the rapid, selective and sensitive evaluation of sulfonamides in contaminated food. PMID:19615505

  18. Environmental fate of two sulfonamide antimicrobial agents in soil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Veterinary antimicrobials have been detected in a number of environmental samples, including agricultural soils. In this study, the persistence and sorption of the sulfonamide sulfamethazine (SMZ) and sulfachloropyridine (SCP) in soil and their potential effects on soil microorganisms were investiga...

  19. Penoxsulam--structure-activity relationships of triazolopyrimidine sulfonamides.

    PubMed

    Johnson, Timothy C; Martin, Timothy P; Mann, Richard K; Pobanz, Mark A

    2009-06-15

    The discovery of the sulfonamide herbicides, which inhibit the enzyme acetolactate synthase (ALS), has resulted in many investigations to exploit their herbicidal activity. One area which proved particularly productive was the N-aryltriazolo[1,5-c]pyrimidine sulfonamides, providing three commercial herbicides, cloransulam-methyl, diclosulam and florasulam. Additional structure-activity investigations by reversing the sulfonamide linkage resulted in the discovery of triazolopyrimidine sulfonamides with cereal crop selectivity and high levels of grass and broadleaf weed control. Research efforts to exploit these high levels of weed activity ultimately led to the discovery of penoxsulam, a new herbicide developed for grass, sedge and broadleaf weed control in rice. Synthetic efforts and structure-activity relationships leading to the discovery of penoxsulam will be discussed. PMID:19464188

  20. Synthesis and biological evaluation of new 2-azetidinones with sulfonamide structures.

    PubMed

    Dragostin, Oana Maria; Lupascu, Florentina; Vasile, Cornelia; Mares, Mihai; Nastasa, Valentin; Moraru, Ramona Florina; Pieptu, Dragos; Profire, Lenuta

    2013-01-01

    New series of N-(arylidene)hydrazinoacetyl sulfonamides 4a1-6, 4b1-6 and N-(4-aryl-3-chloro-2-oxoazetidin-1-yl)aminoacetyl sulfonamides 5a1-6, 5b1-6 were synthesized. The structures of the new derivatives was confirmed using spectral methods (FT-IR, 1H-NMR, 13C-NMR). The antibacterial activities of these compounds against Gram positive (Staphylococcus aureus ATCC 6583, Staphylococcus epidermidis ATCC 12228, Enterococcus faecalis ATCC 25912) and Gram negative (Klebsiella pneumoniae CIP 53153, Proteus vulgaris CIP 104989, Citrobacter freundii CIP 5732, Enterobacter cloacae CIP 103475, Escherichia coli ATCC 25922, Pseudomonas aeruginosa CIP 82118) bacterial strains were evaluated using the broth micro-dilution method. Compound 4a2 displayed the highest antibacterial activity, especially against Staphylococcus epidermidis, Enterococcus faecalis and Pseudomonas aeruginosa. The antioxidant potential of the synthesized compounds was also investigated according to ferric reducing power, total antioxidant activity and DPPH radical scavenging assays. All tested compounds showed excellent antioxidant activity in comparison with sulfadiazine and sulfisoxazole which were used as parent sulfonamides. Moreover, some of them showed an antioxidant activity comparable with that of ascorbic acid. In general, the compounds designed based on a sulfadiazine skeleton (compounds 4a1-6, 5a1-6) are more active than those obtained from sulfisoxazole (compounds 4b1-6, 5b1-6), and the N-(arylidene)hydrazinoacetyl sulfonamide derivatives 4a1-6, 4b1-6 are more active than their azetidionone analogues 5a1-6, 5b1-6. PMID:23567362

  1. Determination of sulfonamide residues in the tissues of food animals using automated precolumn derivatization and liquid chromatography with fluorescence detection.

    PubMed

    Salisbury, Craig D C; Sweet, Jason C; Munro, Roger

    2004-01-01

    A liquid chromatographic method for the determination of sulfachloropyridazine, sulfadiazine, sulfadimethoxine, sulfadoxine, sulfaethoxypyridazine, sulfamethazine, sulfaquinoxaline, and sulfathiazole residues in the muscle, liver, and kidney of food animals using sulfapyridine as internal standard is reported. Tissues are extracted using a modified version of AOAC Official Method 983.31 (Sulfonamide Residues in Animal Tissues). The sample extract is reconstituted in pH 3.0 buffer-acetonitrile (60 + 40) and filtered into an autosampler vial. Using a programmable autosampler of a liquid chromatograph, a portion of the sample is derivatized precolumn with fluorescamine. The sulfonamide derivatives are separated by liquid chromatography using a C18 column with a mobile phase of 0.02M phosphoric acid-acetonitrile (60.5 + 39.5) and detected by fluorescence (excitation, 405 nm; emission, 495 nm). The method was applied to swine and cattle muscle, liver, and kidney; sheep and horse muscle and kidney; and chicken muscle and liver. The mean values for samples fortified with sulfonamides at levels between 0.05 and 0.2 microg/g agreed within 96-99% of spiked levels, with coefficients of variation ranging from 4-10%. The limit of detection (LOD) for all sulfonamides was 0.01 microg/g, with the exception of sulfaquinoxaline, for which the LOD was 0.015 microg/g. PMID:15493686

  2. Multi-residue and multi-class determination of antibiotics in gilthead sea bream (Sparus aurata) by ultra high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Freitas, Andreia; Leston, Sara; Rosa, João; Castilho, Maria da Conceição; Barbosa, Jorge; Rema, Paulo; Pardal, Miguel Ângelo; Ramos, Fernando

    2014-01-01

    This paper describes a method for the determination of 41 antibiotics from seven different classes in gilthead sea bream (Sparus aurata) by ultra-high-performance liquid chromatography with tandem mass spectrometry (UPLC-MS/MS). Sulfonamides, trimethoprim, tetracyclines, macrolides, quinolones, penicillins and chloramphenicol were simultaneously determined. Fourteen procedures for sample treatment were tested and an extraction with acetonitrile and ethylenediaminetetra acetic acid was found to be the best option. The methodology was validated in accordance with Decision 2002/657/EC. Precision in terms of relative standard deviation (RSD) was under 17% for all compounds, and the recoveries ranged from 92% to 111%. CCα and CCβ were determined according to the maximum residue limit or the minimum required performance limit, when necessary. The validation provided evidence that the method was suitable for application in routine analysis for the detection and confirmation of antibiotics in muscle of gilthead sea bream, an important and intensively produced fish in aquaculture. PMID:24512256

  3. Palladium-Catalyzed Site-Selective C-H Functionalization of Weakly Coordinating Sulfonamides: Synthesis of Biaryl Sulfonamides.

    PubMed

    Vanjari, Rajeshwer; Guntreddi, Tirumaleswararao; Singh, Krishna Nand

    2016-03-01

    A novel and site selective C-H functionalization of unsubstituted sulfonamides has been developed for the synthesis of ortho aryl sulfonamides. The reaction involves highly regioselective ortho mono arylation of weakly coordinating SO2 NH2 directing group by means of aryl iodides. Palladium acetate in the presence of silver(I) oxide is found to be the most effective catalytic system. PMID:26763530

  4. [Determination of 14 sulfonamide residues in shrimps by high performance liquid chromatography coupled with post-column derivatization].

    PubMed

    Huang, Dongmei; Huang, Xuanyun; Gu, Runrun; Hui, Yunhua; Tian, Liangliang; Feng, Bing; Zhang, Xuan; Yu, Huijuan

    2014-08-01

    A method for the determination of 14 sulfonamide residues in shrimps by high performance liquid chromatography coupled with post-column derivatization was established. The sulfonamide residues were extracted with ethyl acetate after adding sulfapyridine as internal standard. The extracts were vacuum-concentrated and reverse-extracted by 2 mol/L hydrochloric acid solution for clean-up, and then the hydrochloric acid solution was defatted with n-hex- ane. The solution after filtration was blended with a mixed solution of methanol, acetonitrile and 3. 5 mol/L sodium acetate solution (5:5:20, v/v/v). The sulfonamides were separated on a C18 column by RP-HPLC and on-line derivatized with a fluorescamine and detected with a fluorescence detector. The standard addition method was used for quantitative analysis. The parameters of post-column derivatization system, such as concentration of fluorescamine solution, velocity of reagent solution and reaction temperature, were optimized. The calibration curves of the method showed good linearity in the range of 5 - 200 μg/L. The limits of quantification (LOQ, S/N= 10) were 1.0-5.0 μg/kg for the 14 sulfonamides. The recoveries were 77.8%- 103. 6% in the spiked range of 1. 0-100.0 μg/kg in shrimps with the relative standard deviations of 2.9%-9.1% (n= 6). The results indicated that the method is sensitive, efficient and more accurate. It is suitable for the simultaneous determination of the 14 sulfonamide residues in shrimps. PMID:25434125

  5. Highly sensitive determination of sulfonamides in environmental water samples by sodium dodecylbenzene sulfonate enhanced micro-solid phase extraction combined with high performance liquid chromatography.

    PubMed

    Zhou, Qingxiang; Fang, Zhi

    2015-08-15

    Sulfonamides are important antibiotics, and have achieved great applications. However they also impose serious threat on the environment and human health when they enter into environment by various ways. Present study developed a new determination method for six sulfonamides such as sulfadiazine, sulfamerazine, sulfamethazine, sulfadimethoxine, sulfamethoxazole and sulfafurazole in water samples, which was based on micro-solid phase extraction (μ-SPE) using TiO2 nanotube arrays as the adsorbent in combination with high performance liquid chromatography. Surfactant sodium dodecylbenzene sulfonate (SDBS) was used to enhance the extraction performance in this enrichment procedure. The parameters that affected the extraction efficiency had been investigated. Under the optimal conditions, it was observed that there were good linear relationships between the peak areas and the concentrations of the sulfonamides. The linear ranges were 1-200μg L(-1) for the six sulfonamides with the correlation coefficients in the range of 0.998-0.999. The repeatability of the proposed method was satisfactory in the range of 2.1-4.4% (RSD, n=6). The limits of detection (LODs) were in the range of 0.27-0.6μg L(-1). The proposed method was validated with real environmental samples, and the spiked recoveries were satisfied. These results indicated that the proposed method was a good tool for monitoring sulfonamides in the water samples. PMID:25966398

  6. Determination of sulfonamides by packed column supercritical fluid chromatography with atmospheric pressure chemical ionisation mass spectrometric detection.

    PubMed

    Dost, K; Jones, D C; Davidson, G

    2000-07-01

    Sulfonamide antibiotics are widely used to prevent bacterial infections in livestock, and residues are commonly found in milk and meat. Packed column supercritical fluid chromatography (pSFC) with detection using ultra violet (UV) and atmospheric pressure chemical ionisation (APCI) mass spectrometry (MS) provides a versatile method for the detection and quantification of six major sulfonamides. The APCI mass spectra for all the sulfonamides consisted of protonated molecules at low cone voltages. Increasing the cone voltage led to informative fragmentation patterns, which provided structural information for identification purposes. The pSFC-APCI-MS technique was shown to be linear (r2 > or = 0.999) over the concentration range 0.1-50 micrograms ml-1 using total ion current. The precision and the accuracy of the system and validation of sample preparation are acceptable, with RSD < 2% and relative error 8%. Selected ion monitoring gave detection limits as follows: sulfadiazine 41, sulfamethoxazole 45, sulfamerazine 47, sulfamethizole 59, sulfamethazine 181 and sulfadimethoxine 96 micrograms l-1, which are lower than the amounts permitted in milk products. The APCI pSFC-MS system was shown to have a high degree of reproducibility. The technique was then applied to determine the above sulfonamides in milk. The results obtained show that there are no matrix effects from the milk and that the detection limits remained as stated for the standard solutions. PMID:10984919

  7. Determination of sulfonamides in pork, egg, and chicken using multiwalled carbon nanotubes as a solid-phase extraction sorbent followed by ultra-performance liquid chromatography/tandem mass spectrometry.

    PubMed

    Zhao, Haixiang; Ding, Mingyu; Gao, Yunbao; Deng, Wei

    2014-01-01

    Twelve sulfonamide residues, namely, sulfadiazine, sulfamerazine, sulfamethazine, sulfamonomethoxine, sulfadoxine, sulfamethoxazole, sulfaquinoxaline, sulfadimethoxine, sulfanilamide, sulfathiazole, sulfapyridine, and sulfamethizole were determined in pork tissue, chicken, and eggs by ultra-performance LC/MS/MS after SPE cleanup using multiwalled carbon nanotubes, which permitted extracted samples from animal tissue and eggs to be cleaned up under either normal phase (NP) or reversed phase (RP) conditions or both. In this method, the NP cleanup provided recoveries for nine of the 12 sulfonamides ranging from 71 to 90% and <60% for the remaining three with RSDs lower than 10%. For the RP cleanup method, the recoveries for nine of the 12 sulfonamides ranged from 70 to 94% and <60% for the remaining three with RSDs <11.1%. The two cleanup methods can complement each other to complete the simultaneous analysis of the 12 sulfonamides. PMID:25903004

  8. Multi-residue analysis of 90 emerging contaminants in liquid and solid environmental matrices by ultra-high-performance liquid chromatography tandem mass spectrometry.

    PubMed

    Petrie, Bruce; Youdan, Jane; Barden, Ruth; Kasprzyk-Hordern, Barbara

    2016-01-29

    Reported herein is new analytical methodology for the determination of 90 emerging contaminants (ECs) in liquid environmental matrices (crude wastewater, final effluent and river water). The application of a novel buffer, ammonium fluoride improved signal response for several ECs determined in negative ionisation mode. Most notably the sensitivity of steroid estrogens was improved by 4-5 times in environmental extracts. Method recoveries ranged from 40 to 152% in all matrices and method quantitation limits (MQLs) achieved were <1ngL(-1) for numerous ECs. Development of a microwave assisted extraction (MAE) protocol as an additional sample extraction step for solid matrices enabled 63 ECs to be simultaneously analysed in digested sludge. To the authors knowledge this is considerably more than any previously reported MAE method. Here, MQLs ranged from 0.1-24.1ngg(-1) dry weight. The application of MAE offers several advantages over pressurized liquid extraction including faster sample preparation, lower solvent requirements, and the ability to perform several extractions simultaneously as well as lower purchasing and running costs. To demonstrate the method's sensitivity, application to environmental samples revealed 68 and 40 ECs to be above their respective MQL in liquid environmental samples and digested sludge, respectively. To date, this is the most comprehensive multi-residue analytical method reported in the literature for the determination of ECs in both liquid and solid environmental matrices. PMID:26792447

  9. Multiresidue determination of sulfonamides in edible catfish, shrimp and salmon tissues by high-performance liquid chromatography with postcolumn derivatization and fluorescence detection.

    PubMed

    Gehring, Theresa A; Griffin, Bill; Williams, Rod; Geiseker, Charles; Rushing, Larry G; Siitonen, Paul H

    2006-08-18

    A liquid chromatographic (LC) method for determining 14 sulfonamide (SA) (sulfanilamide, sulfadiazine (SDZ), sulfathiazole, sulfapyridine, sulfamerazine (SMR), sulfamethazine (SMZ), sulfamethizole, sulfamethoxypyridazine, sulfachloropyridazine (SCP), sulfamonomethoxine, sulfadoxine, sulfamethoxazole, sulfadimethoxine (SDM), and sulfaquinoxaline (SQX)) residues in edible catfish, shrimp and salmon tissues was developed and validated at 5, 10 or 20 ng g(-1). The method was then used to determine residues in tissues of catfish, shrimp and salmon dosed with six selected sulfonamides (sulfadiazine, sulfamerazine, sulfamethazine, sulfachloropyridazine, sulfadimethoxine and sulfaquinoxaline). All assays were within U.S. Food and Drug Administration guidelines for recovery and intra-assay variability. The method was developed to determine possible sulfonamide residues in aquacultured catfish, shrimp and salmon produced for food. PMID:16750659

  10. Dispersive solid-phase extraction followed by liquid chromatography-tandem mass spectrometry for the multi-residue analysis of pesticides in raw bovine milk.

    PubMed

    Dagnac, Thierry; Garcia-Chao, Maria; Pulleiro, Paula; Garcia-Jares, Carmen; Llompart, Maria

    2009-05-01

    A fast multi-residue method based on dispersive solid-phase extraction (DSPE) followed by liquid chromatography-tandem mass spectrometry was developed for the simultaneous determination of 44 pesticides in raw bovine milk. Raw bovine milk samples did not percolate through SPE cartridges usually applied for pesticide extraction from homogenized pasteurized milk samples. Therefore, a DSPE technique was implemented and validated for the first time in this work. Graphitized non-porous carbon and C18 modified silica materials were tested both in combination with magnesium sulfate and bonded silica with ethylenediamine-N-propyl phase. The efficiency of the DSPE process was studied at several concentration levels obtaining the higher recoveries with C18 material. The method performance was also assessed and the limits of quantification reached the ng g(-1) level, complying with the most recent maximum residue levels. The DSPE method was also shown to be suited to both the fatty and skimmed fractions issued from raw milk. Finally, the extraction method was successfully applied to the analysis of raw milk samples collected in 23 farms of dairy cattle from NW Spain (Galicia). PMID:19268955

  11. Monodrug efficacies of sulfonamides in prophylaxis for Pneumocystis carinii pneumonia.

    PubMed Central

    Hughes, W T; Killmar, J

    1996-01-01

    A remarkably high rate of adverse events is associated with the use of trimethoprim-sulfamethoxazole in patients with human immunodeficiency virus type 1 infection. We examined the efficacies of sulfonamides alone in the prevention of Pneumocystis carinii pneumonitis, with the assumption that at least some of the adverse events with the drug combination might be due to trimethoprim. With the immunosuppressed rat model, eight sulfonamides were studied at 100, 10, and 1.0 mg/kg/day (10 rats per dosage and drug). P. carinii infection was prevented in all animals (100%) receiving dosages of as little as 1.0 mg of sulfamethoxazole, sulfamethoxypyridazine, and sulfadimethoxine per kg per day, as little as 10 mg of sulfameter, sulfachlorpyridazine, and sulfaquinoxaline per kg per day; and 100 mg of sulfaguanidine and sulfanilamide per kg per day. These studies suggest that a sulfonamide, such as sulfamethoxazole, might provide effective prophylaxis for P. carinii pneumonitis without trimethoprim. PMID:8849260

  12. Importance of sulfonamide moiety in current and future therapy.

    PubMed

    Parasca, Oana Maria; Gheaţă, Florentina; Pânzariu, Andreea; Geangalău, Ioana; Profire, Lenuţa

    2013-01-01

    Sulfonamides and their different derivatives are extensively used in therapy due to their pharmacological properties. Sulfa drugs were amongst the oldest synthesized antimicrobial agents and are still widely used today to treat different microbial infections. Clinical treatment with sulfonamides has regained confidence with the use of a combination of sulfamethoxazole and trimethoprim to treat urinary tract bacterial infections. Today, they are widely used as antimicrobial agents, chiefly because of their low cost, low toxicity and excellent activity against bacterial diseases. Over the course of time, the application of sulfonamides has been extended from their use as antimicrobial agents to anticancer agents, antiglaucoma agents, inhibitors of gamma-secretase, cyclooxgenase-2 and lipoxygenase, anticonvulsivant agents, hypoglycemic agents. PMID:24340546

  13. Investigation of Antigen-Antibody Interactions of Sulfonamides with a Monoclonal Antibody in a Fluorescence Polarization Immunoassay Using 3D-QSAR Models

    PubMed Central

    Wang, Zhanhui; Kai, Zhenpeng; Beier, Ross C.; Shen, Jianzhong; Yang, Xinling

    2012-01-01

    A three-dimensional quantitative structure-activity relationship (3D-QSAR) model of sulfonamide analogs binding a monoclonal antibody (MAbSMR) produced against sulfamerazine was carried out by Distance Comparison (DISCOtech), comparative molecular field analysis (CoMFA), and comparative molecular similarity indices analysis (CoMSIA). The affinities of the MAbSMR, expressed as Log10IC50, for 17 sulfonamide analogs were determined by competitive fluorescence polarization immunoassay (FPIA). The results demonstrated that the proposed pharmacophore model containing two hydrogen-bond acceptors, two hydrogen-bond donors and two hydrophobic centers characterized the structural features of the sulfonamides necessary for MAbSMR binding. Removal of two outliers from the initial set of 17 sulfonamide analogs improved the predictability of the models. The 3D-QSAR models of 15 sulfonamides based on CoMFA and CoMSIA resulted in q2 cv values of 0.600 and 0.523, and r2 values of 0.995 and 0.994, respectively, which indicates that both methods have significant predictive capability. Connolly surface analysis, which mainly focused on steric force fields, was performed to complement the results from CoMFA and CoMSIA. This novel study combining FPIA with pharmacophore modeling demonstrates that multidisciplinary research is useful for investigating antigen-antibody interactions and also may provide information required for the design of new haptens. PMID:22754368

  14. Application of packed porous nanofibers-solid-phase extraction for the detection of sulfonamide residues from environmental water samples by ultra high performance liquid chromatography with mass spectrometry.

    PubMed

    Chen, Rong; Yang, Yingying; Wang, Na; Hao, Lijun; Li, Li; Guo, Xinyan; Zhang, Junchi; Hu, Yuzhu; Shen, Weiyang

    2015-03-01

    Porous electrospun nanofibers, as new materials for solid-phase extraction, were synthesized by electrospinning and coupled with ultra high performance liquid chromatography and mass spectrometry to determine sulfonamide residues in environmental water. Aligned porous polystyrene electrospun nanofibers were fabricated under the mechanism of phase separation. The high-specific surface of these nanofibers (70 m(2)/g) could improve recoveries of the target sulfonamides 4-10 times compared with that of polystyrene nonporous material (3.8 m(2)/g). Under the optimized conditions, 13 sulfonamide residues showed an excellent linear relationship in the range of 0.125-12.5 ng/mL with a linear correlation coefficient (r(2)) greater than 0.99, and the detection limits of sulfonamides were as low as 0.80-5.0 ng/L. Compared to the commercial C18 and HLB columns, the homemade porous nanofibers columns had some merits including simple fabrication and extraction process, short process time and environmental friendliness. The optimized method was applied to eight water samples collected from different livestock farms (Xuzhou, China). The results showed that polystyrene porous nanofibers were promising to preconcentrate sulfonamides of different polarities in the waste water. PMID:25546059

  15. Multi-residue analysis of 26 organochlorine pesticides in Alpinia oxyphylla by GC-ECD after solid phase extraction and acid cleanup.

    PubMed

    Zhao, Xiangsheng; Zhou, Yakui; Kong, Weijun; Gong, Bao; Chen, Deli; Wei, Jianhe; Yang, Meihua

    2016-04-01

    A simple and effective multi-residue method was developed and validated for the analysis of 26 organochlorine pesticide residues in Alpinia oxyphylla by a gas chromatography with an electron capture detector (GC-ECD). The target pesticides were extracted by sonication and cleaned up with florisil solid phase extraction and sulphuric acid. Some crucial parameters, including extraction solvent and time, sorbent type, elute solvent and concentration of sulphuric acid were optimized to improve the performance of sample preparation procedure. The optimized method gave high sensitivity with detection limit ranging from 0.1 to 2.0μg/kg. Matrix-matched calibration was employed for the quantification, and a wide linear range (from 1.0 to 1000μg/kg) with r(2) values ranging from 0.9971 to 0.9998 was obtained. For the majority of the tested pesticides, the average recoveries were in acceptable range (between 70% and 110%) with relative standard deviation values below 15.0%. Matrix effect was evaluated for target compounds through the study of ratio of peak area obtained in the solvent and blank matrix. The proposed method was applied to simultaneously analyze 26 pesticides in 55 batches of Alpinia oxyphylla samples. 3 samples were found to be positive with four pesticides (α-BHC, quintozene, trans-chlordane and op'-DDD), which were confirmed by gas chromatography-mass spectrometry (GC-MS) in selective ion monitoring (SIM) mode. PMID:26990736

  16. Automated multi-plug filtration cleanup for liquid chromatographic-tandem mass spectrometric pesticide multi-residue analysis in representative crop commodities.

    PubMed

    Qin, Yuhong; Zhang, Jingru; Zhang, Yuan; Li, Fangbing; Han, Yongtao; Zou, Nan; Xu, Haowei; Qian, Meiyuan; Pan, Canping

    2016-09-01

    An automated multi-plug filtration cleanup (m-PFC) method on modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) extracts was developed. The automatic device was aimed to reduce labor-consuming manual operation workload in the cleanup steps. It could control the volume and the speed of pulling and pushing cycles accurately. In this work, m-PFC was based on multi-walled carbon nanotubes (MWCNTs) mixed with other sorbents and anhydrous magnesium sulfate (MgSO4) in a packed tip for analysis of pesticide multi-residues in crop commodities followed by liquid chromatography with tandem mass spectrometric (LC-MS/MS) detection. It was validated by analyzing 25 pesticides in six representative matrices spiked at two concentration levels of 10 and 100μg/kg. Salts, sorbents, m-PFC procedure, automated pulling and pushing volume, automated pulling speed, and pushing speed for each matrix were optimized. After optimization, two general automated m-PFC methods were introduced to relatively simple (apple, citrus fruit, peanut) and relatively complex (spinach, leek, green tea) matrices. Spike recoveries were within 83 and 108% and 1-14% RSD for most analytes in the tested matrices. Matrix-matched calibrations were performed with the coefficients of determination >0.997 between concentration levels of 10 and 1000μg/kg. The developed method was successfully applied to the determination of pesticide residues in market samples. PMID:27507726

  17. Multi-residue analysis of 80 environmental contaminants in honeys, honeybees and pollens by one extraction procedure followed by liquid and gas chromatography coupled with mass spectrometric detection.

    PubMed

    Wiest, Laure; Buleté, Audrey; Giroud, Barbara; Fratta, Cédric; Amic, Sophie; Lambert, Olivier; Pouliquen, Hervé; Arnaudguilhem, Carine

    2011-08-26

    One of the factors that may explain nowadays honeybees' colonies losses is the increasing presence of chemicals in the environment. The aim of this study is to obtain a global view of the presence of environmental contaminants in beehives and, develop a fast, cheap and sensitive tool to analyze environmental contaminants in apiarian matrices. A multi residue analysis was developed to quantify 80 environmental contaminants, pesticides and veterinary drugs, belonging to different chemical classes, in honeys, honeybees and pollens. It consists in a single extraction, based on a modified "QuEChERS method", followed by gas chromatography coupled with Time of Flight mass spectrometry (GC-ToF) and liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). The "QuEChERS method" combines salting-out liquid-liquid extraction with acetonitrile and a dispersive-SPE clean up. It was adjusted to honey and especially to honeybee and pollen, by adding a small fraction of hexane in acetonitrile to eliminate lipids that interfere with mass spectrometry analysis. This method, combined with accurate and sensitive detection, allowed quantification and confirmation at levels as low as 10 ng/g, with recoveries between 60 and 120%. Application to more than 100 samples of each matrix was achieved for a global view of pesticide presence in the honeybee environment. Relatively high percentages of honeys, honeybees and pollens were found to be contaminated by pesticides used to combat varroa but also by fungicides like carbendazim and ubiquitous contaminants. PMID:21783197

  18. Comparative mobility of sulfonamides and bromide tracer in three soils

    USGS Publications Warehouse

    Kurwadkar, S.T.; Adams, C.D.; Meyer, M.T.; Kolpin, D.W.

    2011-01-01

    In animal agriculture, sulfonamides are one of the routinely used groups of antimicrobials for therapeutic and sub-therapeutic purposes. It is observed that, the animals when administered the antimicrobials, often do not completely metabolize them; and excrete the partially metabolized forms into the environment. Due to the continued use of antimicrobials and disposal of untreated waste, widespread occurrence of partially metabolized antimicrobials in aquatic and terrestrial environments has been reported in various scientific journals. In this research, the mobility of two sulfonamides - sulfamethazine (SMN), sulfathiazole (STZ) and a conservative bromide tracer was investigated in three soils collected from regions in the United States with large number of concentrated animal-feed operations. Results of a series of column studies indicate that the mobility of these two sulfonamides was dependent on pH, soil charge density, and contact time. At low pH and high charge density, substantial retention of sulfonamides was observed in all three soils investigated, due to the increased fraction of cationic and neutral forms of the sulfonamides. Conversely, enhanced mobility was observed at high pH, where the sulfonamides are predominantly in the anionic form. The results indicate that when both SMN and STZ are predominantly in anionic forms, their mobility approximates the mobility of a conservative bromide tracer. This observation is consistent for the mobility of both SMN and STZ individually, and also in the presence of several other antimicrobials in all three soils investigated. Higher contact time indicates lower mobility due to increased interaction with soil material. ?? 2011.

  19. Discovery of Tertiary Sulfonamides as Potent Liver X Receptor Antagonists

    SciTech Connect

    Zuercher, William J.; Buckholz†, Richard G.; Campobasso, Nino; Collins, Jon L.; Galardi, Cristin M.; Gampe, Robert T.; Hyatt, Stephen M.; Merrihew, Susan L.; Moore, John T.; Oplinger, Jeffrey A.; Reid, Paul R.; Spearing, Paul K.; Stanley, Thomas B.; Stewart, Eugene L.; Willson, Timothy M.

    2010-08-12

    Tertiary sulfonamides were identified in a HTS as dual liver X receptor (LXR, NR1H2, and NR1H3) ligands, and the binding affinity of the series was increased through iterative analogue synthesis. A ligand-bound cocrystal structure was determined which elucidated key interactions for high binding affinity. Further characterization of the tertiary sulfonamide series led to the identification of high affinity LXR antagonists. GSK2033 (17) is the first potent cell-active LXR antagonist described to date. 17 may be a useful chemical probe to explore the cell biology of this orphan nuclear receptor.

  20. Simultaneous analysis of 16 sulfonamide and trimethoprim antibiotics in environmental waters by liquid chromatography-electrospray tandem mass spectrometry.

    PubMed

    Chang, Hong; Hu, Jianying; Asami, Mari; Kunikane, Shoichi

    2008-05-01

    A sensitive liquid chromatography-electrospray tandem mass spectrometry method combined with solid-phase extraction and silica cartridge cleanup was established for 16 sulfonamides and trimethoprim in various water matrices. Signal suppression of all target analytes in sewage treatment plant influent, effluent and river water was improved by this method developed in this study. The method detection limits for 17 analytes were 20-200 pg/L for influent, 16-120 pg/L for effluent and 8.0-60 pg/L for river water with overall mean recoveries of 62-102% in all studied matrices. This method was used to analyze residual sulfonamides and trimethoprim in wastewater and river samples from Japan, and 8 analytes (0.08 (sulfadimethoxine)-161 ng/L (sulfapyridine) in wastewater and 10 (0.03 (sulfamethizol)-8.9 ng/L (sulfaquinoxaline) in river samples were detected. PMID:18395732

  1. The metabolic rationale for a lack of cross-reactivity between sulfonamide antimicrobials and other sulfonamide-containing drugs.

    PubMed

    Lehmann, David F

    2012-06-01

    Sulfonamide antimicrobials (sulfamethoxazole) contain an arylamine group, oxidized by CYP2C9 to the hydroxylamine with subsequent auto-oxidation to a highly reactive [-nitroso-] intermediate is a necessary (if not sufficient) cause of drug hypersensitivity. Accordingly, xenobiotics that do not contain an arylamine cannot generate this reactive intermediate and do not cross react with sulfonamide antimicrobials. Despite this well-attested observation, product labeling and direct-to-consumer advertising for non-arylamine therapeutic classes of drugs containing the sulfonamido- functional group persist with a warning of the potential for cross-reactivity. It is hoped that by offering an explicit rationale for the lack of cross-reactivity will provide medical practitioners with a level comfort to proceed with prescribing medications such as thiazide diuretics and celecoxib for patients with a history of hypersensitivity to sulfonamide antimicrobials. PMID:23157194

  2. The antibacterial activity of some sulfonamides and sulfonyl hydrazones, and 2D-QSAR study of a series of sulfonyl hydrazones

    NASA Astrophysics Data System (ADS)

    Aslan, H. Güzin; Özcan, Servet; Karacan, Nurcan

    2012-12-01

    Benzenesulfonicacid-1-methylhydrazide (1) and its four aromatic sulfonyl hydrazone derivatives (1a-1d), N-(3-amino-2-hydroxypropyl)benzene sulfonamide (2) and N-(2-hydroxyethyl)benzenesulfonamide (3) were synthesized and their structures were determined by IR, 1H NMR, 13C NMR, and LCMS techniques. Antibacterial activities of new synthesized compounds were evaluated against various bacteria strains by microdilution and disk diffusion methods. The experimental results show that presence of OH group on sulfonamides reduces the antimicrobial activity, and antimicrobial activities of the sulfonyl hydrazones (1a-1d) are smaller than that of the parent sulfonamide (1), except Candida albicans. In addition, 2D-QSAR analysis was performed on 28 aromatic sulfonyl hydrazones as antimicrobial agents against Escherichia coli and Staphylococcus aureus. In the QSAR models, the most important descriptor is total point-charge component of the molecular dipole for E. coli, and partial negative surface area (PNSA-1) for S. aureus.

  3. 21 CFR 862.3850 - Sulfonamide test system.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Sulfonamide test system. 862.3850 Section 862.3850 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Toxicology Test Systems §...

  4. 21 CFR 862.3850 - Sulfonamide test system.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Sulfonamide test system. 862.3850 Section 862.3850 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Toxicology Test Systems §...

  5. 21 CFR 862.3850 - Sulfonamide test system.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Sulfonamide test system. 862.3850 Section 862.3850 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Toxicology Test Systems §...

  6. 21 CFR 862.3850 - Sulfonamide test system.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Sulfonamide test system. 862.3850 Section 862.3850 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Toxicology Test Systems §...

  7. 21 CFR 862.3850 - Sulfonamide test system.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Sulfonamide test system. 862.3850 Section 862.3850 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Toxicology Test Systems §...

  8. Lipoamide channel-binding sulfonamides selectively inhibit mycobacterial lipoamide dehydrogenase†,#

    PubMed Central

    Bryk, Ruslana; Arango, Nancy; Maksymiuk, Christina; Balakrishnan, Anand; Wu, Ying-Ta; Wong, Chi-Huey; Masquelin, Thierry; Hipskind, Philip; Lima, Christopher D.; Nathan, Carl

    2014-01-01

    Tuberculosis remains a global health emergency that calls for treatment regimens directed at new targets. Here we explored lipoamide dehydrogenase, a metabolic and detoxifying enzyme in Mycobacterium tuberculosis whose deletion drastically impairs Mtb's ability to establish infection in the mouse. Upon screening over 1,600,000 compounds, we identified N-methylpyridine 3-sulfonamides as potent and species-selective inhibitors of Mtb Lpd, affording over 1,000-fold selectivity versus the human homolog. The sulfonamides demonstrated low nanomolar affinity and bound at the lipoamide channel in an Lpd-inhibitor co-crystal. Their selectivity could be attributed, at least partially, to hydrogen bonding of the sulfonamide amide oxygen with the species-variant Arg93 in the lipoamide channel. Although potent and selective, the sulfonamides did not enter mycobacteria, as determined by their inability to accumulate in Mtb to effective levels and produce changes in intracellular metabolites. This work demonstrates that high potency and selectivity can be achieved at the lipoamide binding site of Mtb Lpd, a site different from the NAD+/NADH pocket targeted by previously reported species-selective triazaspirodimethoxybenzoyl inhibitors. PMID:24251446

  9. Effect of humic acid (HA) on sulfonamide sorption by biochars.

    PubMed

    Lian, Fei; Sun, Binbin; Chen, Xi; Zhu, Lingyan; Liu, Zhongqi; Xing, Baoshan

    2015-09-01

    Effect of quantity and fractionation of loaded humic acid (HA) on biochar sorption for sulfonamides was investigated. The HA was applied in two different modes, i.e. pre-coating and co-introduction with sorbate. In pre-coating mode, the polar fractions of HA tended to interact with low-temperature biochars via H-bonding, while the hydrophobic fractions were likely to be adsorbed by high-temperature biochars through hydrophobic and π-π interactions, leading to different composition and structure of the HA adlayers. The influences of HA fractionation on biochar sorption for sulfonamides varied significantly, depending on the nature of interaction between HA fraction and sorbate. Meanwhile, co-introduction of HA with sulfonamides revealed that the effect of HA on sulfonamide sorption was also dependent on HA concentration. These findings suggest that the amount and fractionation of adsorbed HA are tailored by the surface properties of underlying biochars, which differently affect the sorption for organic contaminants. PMID:26057361

  10. Sorption, fate, and mobility of sulfonamides in soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sulfonamides (SAs) are one of the broadly used antibiotics in domestic animal operations and have a notable potential of entering the environment through animal manure management practices. In this study, sulfamethazine (SMZ) was used as a prototype to study the sorption, fate, and transport of SAs...

  11. Multi-residue enantiomeric analysis of human and veterinary pharmaceuticals and their metabolites in environmental samples by chiral liquid chromatography coupled with tandem mass spectrometry detection.

    PubMed

    Camacho-Muñoz, Dolores; Kasprzyk-Hordern, Barbara

    2015-12-01

    Enantiomeric profiling of chiral pharmacologically active compounds (PACs) in the environment has hardly been investigated. This manuscript describes, for the first time, a multi-residue enantioselective method for the analysis of human and veterinary chiral PACs and their main metabolites from different therapeutic groups in complex environmental samples such as wastewater and river water. Several analytes targeted in this paper have not been analysed in the environment at enantiomeric level before. These are aminorex, carboxyibuprofen, carprofen, cephalexin, 3-N-dechloroethylifosfamide, 10,11-dihydro-10-hydroxycarbamazepine, dihydroketoprofen, fenoprofen, fexofenadine, flurbiprofen, 2-hydroxyibuprofen, ifosfamide, indoprofen, mandelic acid, 2-phenylpropionic acid, praziquantel and tetramisole. The method is based on chiral liquid chromatography utilising a chiral α1-acid glycoprotein column and tandem mass spectrometry detection. Excellent chromatographic separation of enantiomers (Rs≥1.0) was achieved for chloramphenicol, fexofenadine, ifosfamide, naproxen, tetramisole, ibuprofen and their metabolites: aminorex and dihydroketoprofen (three of four enantiomers), and partial separation (Rs = 0.7-1.0) was achieved for ketoprofen, praziquantel and the following metabolites: 3-N-dechloroethylifosfamide and 10,11-dihydro-10-hydroxycarbamazepine. The overall performance of the method was satisfactory for most of the compounds targeted. Method detection limits were at low nanogram per litre for surface water and effluent wastewater. Method intra-day precision was on average under 20% and sample pre-concentration using solid phase extraction yielded recoveries >70% for most of the analytes. This novel, selective and sensitive method has been applied for the quantification of chiral PACs in surface water and effluent wastewater providing excellent enantioresolution of multicomponent mixtures in complex environmental samples. It will help with better understanding

  12. Determination of eight sulfonamides in bovine kidney by liquid chromatography/tandem mass spectrometry with on-line extraction and sample clean-up.

    PubMed

    Van Eeckhout, N; Perez, J C; Van Peteghem, C

    2000-01-01

    A sensitive, high performance liquid chromatography/tandem mass spectrometric (i.e. mass spectrometry/mass spectrometry; LC/MS/MS) method with on-line extraction and sample clean-up for the screening and confirmation of residues of sulfonamides in kidney is described. The sulfonamides are extracted from homogenized kidney with methanol. After centrifugation of the extract, an aliquot of the extract is directly injected on the LC/MS/MS system with further extraction and clean-up of the sample on-line. Detection of the analytes was achieved by positive electrospray ionization (ESI) followed by multiple reaction monitoring. For each sulfonamide the collisional decomposition of the protonated molecule to a common, abundant fragment ion was monitored. The method has been validated for sulfadimethoxine, sulfaquinoxaline, sulfamethazine, sulfamerazine, sulfathiazole, sulfamethoxazole, sulfadiazine and sulfapyridine. Calibration curves resulting from spiked blank kidney samples at the 10-200 microg/kg level showed good linear correlation. At the level of 50, 100 and 200 microg/kg both within- and between-day precision, as measured by relative standard deviation (RSD), were less than 16%. The limits of detection (LODs) ranged from 5 to 13.5 microg/kg. The recoveries ranged from 78 to 82%. The procedure provides a rapid, reliable and sensitive method for the determination of residues of sulfonamides in bovine kidney. The advantage of this method over existing methods is its decreased sample preparation and analysis time, which makes the method more suitable for routine analysis. PMID:11114046

  13. Determination of sulfonamides in beeswax by liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Mitrowska, Kamila; Antczak, Maja

    2015-12-01

    The manuscript presents the development of a new method for the quantification of 16 sulfonamides in beeswax. Different sample preparation techniques were tested and modified to maximise the recovery of the target analytes and minimise the amount of coeluted impurities under conditions that provide reproducible results. The proposed method consisted of melting and dilution of beeswax in a mixture of n-hexane and isopropanol followed by extraction with 2% acetic acid. The extract was cleaned up by solid-phase extraction using strong cation exchange phase. Determination of the sulfonamides was achieved by liquid chromatography coupled to tandem mass spectrometry with the use of a pentafluorophenyl analytical column and applying a gradient elution with acetonitrile and 0.01% acetic acid as mobile phases. The limits of detection and limits of quantification ranged from 1 to 2μg/kg and from 2 to 5μg/kg, respectively. The recoveries varied between 65.2% and 117.8% while coefficient of variation of the method was less than 24.2% under intermediate precision conditions. Finally, the method was applied to the analysis of real samples of beeswax from beekeepers and commercial foundations manufacturers. PMID:26554312

  14. Determination of antibiotics (tetracyclines and sulfonamides) in biosolids by pressurized liquid extraction and liquid chromatography-tandem mass spectrometry.

    PubMed

    Pamreddy, Annapurna; Hidalgo, Manuela; Havel, Josef; Salvadó, Victòria

    2013-07-12

    A robust and sensitive analytical method is developed to quantitatively determine tetracyclines and sulfonamides, two major antibiotic classes, in sewage sludge. The antibiotic agents, oxytetracycline, tetracycline, dioxycycline, chlorotetracycline, sulfathiazole, sulfapyridine, sulfamethazine and sulfamethoxazole, were extracted using pressurized liquid extraction (PLE) with citric acid at pH 3 and methanol (1:1 v/v). Clean-up of the extracts was performed by solid phase extraction (SPE) with hydrophilic-lipophilic balance cartridges. Identification and quantification of the compounds is by liquid chromatography-tandem mass spectrometry in multiple reaction monitoring (MRM) mode. High recoveries ranging from 90.4 to 99.9% for sulfonamides and 96.2 to 100.9% for the tetracyclines are obtained. Method detection limits (MDLs) range from 0.6 to 4.2 ng/g for sulfonamides and 3.2 to 13 ng/g for tetracyclines. After validation, the method is applied to the analysis of sludges collected from different WWTPs in Spain. PMID:23755983

  15. Synthesis of organometallic-based biologically active compounds: In vitro antibacterial, antifungal and cytotoxic properties of some sulfonamide incorporated ferrocences.

    PubMed

    Chohan, Zahid H

    2009-02-01

    Sulfonamides incorporated ferrocene (SIF) have been synthesized by the condensation reaction of sulfonamides (sulfanilamide, sulfathiazole or sulfamethaxazole) with 1,1'-diacetylferrocene. The synthesized compounds (SIF(1)-SIF(4)) have been characterized by their physical, spectral and analytical properties and have been screened for their in vitro antibacterial properties against pathogenic bacterial strains e.g., Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis Staphylococcus aureus and Salmonella typhi and for antifungal activity against Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani and Candida glaberata using Agar-well diffusion method. Most of the compounds showed good antibacterial activity whereas, all the compounds exhibited significant antifungal activity. Brine shrimp bioassay was also carried out for in vitro cytotoxic properties against Artemia salina. PMID:18608785

  16. Multi-residue determination of 115 veterinary drugs and pharmaceutical residues in milk powder, butter, fish tissue and eggs using liquid chromatography-tandem mass spectrometry.

    PubMed

    Dasenaki, Marilena E; Thomaidis, Nikolaos S

    2015-06-23

    A simple and sensitive multi-residue method for the determination of 115 veterinary drugs and pharmaceuticals, belonging in more than 20 different classes, in butter, milk powder, egg and fish tissue has been developed. The method involves a simple generic solid-liquid extraction step (solvent extraction, SE) with 0.1% formic acid in aqueous solution of EDTA 0.1% (w/v)-acetonitrile (ACN)-methanol (MeOH) (1:1:1, v/v) with additional ultrasonic-assisted extraction. Precipitation of lipids and proteins was promoted by subjecting the extracts at very low temperature (-23°C) for 12h. Further cleanup with hexane ensures fat removal from the matrix. Analysis was performed by liquid chromatography coupled with electrospray ionization and tandem mass spectrometry (LC-ESI-MS/MS). Two separate runs were performed for positive and negative ionization in multiple reaction monitoring mode (MRM). Particular attention was devoted to extraction optimization: different sample-to-extracting volume ratios, different concentrations of formic acid in the extraction solvent and different ultrasonic extraction temperatures were tested in butter, egg and milk powder samples. The method was also applied in fish tissue samples. It was validated, on the basis of international guidelines, for all four matrices. Quantitative analysis was performed by means of standard addition calibration. For over 80% of the analytes, the recoveries were between 50% and 120% in all matrices studied, with RSD values in the range of 1-18%. Limits of detection (LODs) and quantification (LOQs) ranged from 0.008 μg kg(-1) (oxfendazole in butter) to 3.15 μg kg(-1) (hydrochlorthiazide in egg). The evaluated method provides reliable screening, quantification, and identification of 115 veterinary drug and pharmaceutical residues in foods of animal origin and has been successfully applied in real samples. PMID:26092343

  17. Determination of the total content of some sulfonamides in milk using solid-phase extraction coupled with off-line derivatization and spectrophotometric detection.

    PubMed

    Dmitrienko, Stanislava G; Kochuk, Elena V; Tolmacheva, Veronika V; Apyari, Vladimir V; Zolotov, Yury A

    2015-12-01

    A simple screening method for isolation and determination of the total content of some sulfonamides in milk using solid-phase extraction and a color reaction is described. This procedure is based on SPE of sulfonamides on hypercrosslinked polystyrene, elution with acetonitrile and off-line derivatization with p-dimethylaminocinnamaldehyde in acetonitrile followed by spectrophotometric determination. The reaction produces intense violet-red color and can be easily used both for quantitation of sulfonamides using spectrophotometry and for naked-eye semi-quantitative estimation. Maximum absorption of the reaction product was determined at 540 nm. The Lambert-Beer's law was obeyed in the range of 0.07-3.0 μg mL(-1) in eluate, with the squared correlation coefficient (R(2)) of 0.9875-0.9995, and the relative standard deviation (RSD) of 3-4%. The limits of SAs detection using preconcentration were of 0.02-0.03 μg mL(-1). The proposed method can be recommended as a routine screening method for quantitation of sulfonamides in milk. PMID:26041163

  18. Studies on the extraction of sulfonamides from agricultural soils.

    PubMed

    Raich-Montiu, J; Beltrán, J L; Prat, M D; Granados, M

    2010-05-01

    The extraction of six sulfonamides (sulfadiazine, sulfadimidine, sulfathiazole, sulfachloropiridazine, sulfadimethoxine, and sulfaquinoxaline) from soils with different physicochemical characteristics and at several aging times was investigated. Conventional mechanical shaking, microwave-assisted extraction, ultrasound probe-assisted extraction and pressurized liquid extraction techniques were evaluated. The four techniques provided similar results when applied to freshly contaminated soils. However, microwave-assisted extraction was the most suitable to extract sulfonamide aged residues from soils. Microwave-assisted extraction was applied to eight soils aged for 3 months, using acetonitrile:buffer pH 9 (20:80) as the extraction solvent, and recoveries ranged from 15-25% for STZ to 42-64% for SDM. PMID:20217396

  19. Determination of sulfonamides in swine meat by immunoaffinity chromatography.

    PubMed

    Li, J S; Li, X W; Yuan, J X; Wang, X; Li, J S; Li, X W; Yuan, J X; Wang, X

    2000-01-01

    A procedure was developed for the preparation of anti-sulfonamide (SA) group-specific antibodies and immunosorbents. Sulfonamide haptens and conjugates were synthesized by building spacer arms on an N1 group of 4-aminobenzensulfonamide. The anti-SA group-specific antibodies and immunosorbents were prepared successfully. After extraction with methanol-water (8 + 2), sulfamonomethoxine, sulfadimethoxine, and sulfaquinoxaline were cleaned up on immunoaffinity columns and determined by reversed-phase liquid chromatography with UV detection at 270 nm. The recoveries from fortified swine meat (10-100 microg/kg) ranged from 70.8 to 94.1%, with coefficients of variation of 3.4-12.9%. Limits of detection were 1-2 microg/kg. PMID:10995109

  20. Spatial analysis and source profiling of beta-agonists and sulfonamides in Langat River basin, Malaysia.

    PubMed

    Sakai, Nobumitsu; Yusof, Roslan Mohd; Sapar, Marni; Yoneda, Minoru; Mohd, Mustafa Ali

    2016-04-01

    Beta-agonists and sulfonamides are widely used for treating both humans and livestock for bronchial and cardiac problems, infectious disease and even as growth promoters. There are concerns about their potential environmental impacts, such as producing drug resistance in bacteria. This study focused on their spatial distribution in surface water and the identification of pollution sources in the Langat River basin, which is one of the most urbanized watersheds in Malaysia. Fourteen beta-agonists and 12 sulfonamides were quantitatively analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). A geographic information system (GIS) was used to visualize catchment areas of the sampling points, and source profiling was conducted to identify the pollution sources based on a correlation between a daily pollutant load of the detected contaminant and an estimated density of human or livestock population in the catchment areas. As a result, 6 compounds (salbutamol, sulfadiazine, sulfapyridine, sulfamethazine, sulfadimethoxine and sulfamethoxazole) were widely detected in mid catchment areas towards estuary. The source profiling indicated that the pollution sources of salbutamol and sulfamethoxazole were from sewage, while sulfadiazine was from effluents of cattle, goat and sheep farms. Thus, this combination method of quantitative and spatial analysis clarified the spatial distribution of these drugs and assisted for identifying the pollution sources. PMID:26799806

  1. Confirmation of 13 sulfonamides in honey by liquid chromatography-tandem mass spectrometry for monitoring plans: validation according to European Union Decision 2002/657/EC.

    PubMed

    Dubreil-Chéneau, Estelle; Pirotais, Yvette; Verdon, Eric; Hurtaud-Pessel, Dominique

    2014-04-25

    A rapid and reliable liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the simultaneous confirmation of 13 sulfonamides in honey was developed and fully validated in accordance with the European Commission Decision No 2002/657/EC. The validation scheme was built in accordance with the target level of 50μgkg(-1) for all analytes. The sulfonamides investigated were as follows: sulfaguanidine (SGN), sulfanilamide (SNL), sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethizole (SMZ), sulfadimerazine (SDM), sulfamonomethoxine (SMNM), sulfamethoxypiridazine (SMP), sulfadoxine (SDX), sulfamethoxazole (SMX), sulfaquinoxaline (SQX) and sulfadimethoxine (SDT). Several extraction procedures were investigated during the development phase. Finally, the best results were obtained with a procedure using acidic hydrolysis and cation exchange purification. Chromatographic separation was achieved on a C18 analytical column. Matrix effects were also investigated. Data acquisition implemented for the confirmatory purpose was performed by monitoring 2 MRM transitions per analyte under the positive electrospray mode. Mean relative recoveries ranged from 85.8% to 110.2% and relative standard deviations lying between 2.6% and 19.8% in intra-laboratory reproducibility conditions. The decision limits (CCα) ranged from 1.8 to 15.5μgkg(-1). High resolution mass spectrometry was used to investigate the possible formation of sulfonamide metabolites in honey. The validation results proved that the method is suitable for the screening and confirmatory steps as implemented for the French monitoring residue plan for sulfonamides residue control in honeybees. PMID:24666935

  2. Binding of Sulfonamide Antibiotics to CTABr Micelles Characterized Using (1)H NMR Spectroscopy.

    PubMed

    Sarker, Ashish K; Cashin, Patrick J; Balakrishnan, Vimal K; Exall, Kirsten; Buncel, Erwin; Brown, R Stephen

    2016-08-01

    Interactions of nine sulfonamide antibiotics (sulfadoxine, sulfathiazole, sulfamethoxazole, sulfamerazine, sulfadiazine, sulfamethazine, sulfacetamide, sulfaguanidine, and sulfanilamide) with cetyltrimethylamonium bromide (CTABr) micelles were examined using (1)H NMR spectroscopy. Seven of the nine provided a significant change in the (1)H NMR chemical shift such that the magnitude and direction (upfield vs downfield) of the chemical shift could be used to propose a locus and orientation of the sulfonamide within the micelle structure. The magnitude of the chemical shift was used to estimate the binding constant for seven sulfonamides with CTABr micelles, providing values and an overall pattern consistent with previous studies of these sulfonamides. PMID:27391918

  3. Application of a hybrid ordered mesoporous silica as sorbent for solid-phase multi-residue extraction of veterinary drugs in meat by ultra-high-performance liquid chromatography coupled to ion-trap tandem mass spectrometry.

    PubMed

    Casado, Natalia; Morante-Zarcero, Sonia; Pérez-Quintanilla, Damián; Sierra, Isabel

    2016-08-12

    A quick, sensitive and selective analytical reversed-phase multi-residue method using ultra-high performance liquid chromatography coupled to an ion-trap mass spectrometry detector (UHPLC-IT-MS/MS) operating in both positive and negative ion mode was developed for the simultaneous determination of 23 veterinary drug residues (β-blockers, β-agonists and Non-Steroidal Anti-inflammatory Drugs (NSAIDs)) in meat samples. The sample treatment involved a liquid-solid extraction followed by a solid-phase extraction (SPE) procedure. SBA-15 type mesoporous silica was synthetized and modified with octadecylsilane, and the resulting hybrid material (denoted as SBA-15-C18) was applied and evaluated as SPE sorbent in the purification of samples. The materials were comprehensively characterized, and they showed a high surface area, high pore volume and a homogeneous distribution of the pores. Chromatographic conditions and extraction procedure were optimized, and the method was validated according to the Commission Decision 2002/657/EC. The method detection limits (MDLs) and the method quantification limits (MQLs) were determined for all the analytes in meat samples and found to range between 0.01-18.75μg/kg and 0.02-62.50μg/kg, respectively. Recoveries for 15 of the target analytes ranged from 71 to 98%. In addition, for comparative purpose SBA-15-C18 was evaluated towards commercial C18 amorphous silica. Results revealed that SBA-15-C18 was clearly more successful in the multi-residue extraction of the 23 mentioned analytes with higher recovery values. The method was successfully tested to analyze prepacked preparations of mince bovine meat. Traces of propranolol, ketoprofen and diclofenac were detected in some samples. PMID:27412322

  4. Transport of sulfonamide antibiotics in small fields during monsoon season

    NASA Astrophysics Data System (ADS)

    Park, J. Y.; Huwe, B.; Kolb, A.; Tenhunen, J.

    2012-04-01

    Transport and fate of 3 sulfonamide antibiotics (sulfamethoxazole, sulfadimethoxine and sulfamethazine) were studied in small agricultural land during monsoon period. The experiment has been conducted in 2 typical sandy loam potato fields of South Korea after application of the veterinary antibiotics and bromide. Precipitation was measured by AWS (Automatic Weather Station) near the fields during the whole monsoon season. Runoff generation was estimated by multislot divisors in combination with pressure sensor. Concentration of the target antibiotics and the conservative tracer in runoff, soil-water and soil was determined using HPLC-MS-MS and Br selected electrode. Transport simulation has been performed with Hydrus-2D program which can consider soil characteristics, climate condition, adsorption/desorption and degradation. Results from the measurements and modeling focus on the role of heavy rainfall, of related the ratio of runoff and infiltration in terms of the selected antibiotics distribution and fate. Bromide on topsoil was moved into soil as increasing rainfall loading. On the contrary, the sulfonamides were relatively retarded in upper soil layer owing to adsorption onto soil particles. Different patterns of runoff were observed, and slope and rain intensity was representative factor in this study. Distribution of target pharmaceuticals was strongly dependent on constitution of furrow and ridge in the agricultural fields. Modeling results positively matched with background studies that describe physico-chemical properties of the sulfonamides, interaction between soil and the antibiotic group, solute transport through vadose zone and runoff induction by storm events.

  5. Biosolid-borne tetracyclines and sulfonamides in plants.

    PubMed

    Mathews, Shiny; Reinhold, Dawn

    2013-07-01

    Tetracyclines and sulfonamides used in human and animal medicine are released to terrestrial ecosystems from wastewater treatment plants or by direct manure application. The interactions between plants and these antibiotics are numerous and complex, including uptake and accumulation, phytometabolism, toxicity responses, and degradation in the rhizosphere. Uptake and accumulation of antibiotics have been studied in plants such as wheat, maize, potato, vegetables, and ornamentals. Once accumulated in plant tissue, organic contaminants can be metabolized through a sequential process of transformation, conjugation through glycosylation and glutathione pathways, and ultimately sequestration into plant tissue. While studies have yet to fully elucidate the phytometabolism of tetracyclines and sulfonamides, an in-depth review of plant and mammalian studies suggest multiple potential transformation and conjugation pathways for tetracyclines and sulfonamides. The presence of contaminants in the vicinity or within the plants can elicit stress responses and defense mechanisms that can help tolerate the negative effects of contaminants. Antibiotics can change microbial communities and enzyme activity in the rhizosphere, potentially inducing microbial antibiotic resistance. On the other hand, the interaction of microbes and root exudates on pharmaceuticals in the rhizosphere can result in degradation of the parent molecule to less toxic compounds. To fully characterize the environmental impacts of increased antibiotic use in human medicine and animal production, further research is essential to understand the effects of different antibiotics on plant physiology and productivity, uptake, translocation, and phytometabolism of antibiotics, and the role of antibiotics in the rhizosphere. PMID:23591931

  6. Multi-residue determination of pharmaceutical and personal care products in vegetables.

    PubMed

    Wu, Xiaoqin; Conkle, Jeremy Landon; Gan, Jay

    2012-09-01

    Treated wastewater irrigation and biosolid amendment are increasingly practiced worldwide and contamination of plants, especially produces that may be consumed raw by humans, by pharmaceutical and personal care products (PPCPs), is an emerging concern. A sensitive method was developed for the simultaneous measurement of 19 frequently-occurring PPCPs in vegetables using high-performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS) for detection, combined with ultrasonic extraction and solid phase extraction (SPE) cleanup for sample preparation. Deuterated standards were used as surrogates to quantify corresponding analytes. The corrected recoveries ranged between 87.1 and 123.5% for iceberg lettuce, with intra- and inter-day variations less than 20%, and the method detection limits (MDLs) in the range of 0.04-3.0 ng g⁻¹ dry weight (dw). The corrected recoveries were equally good when the method was used on celery, tomato, carrot, broccoli, bell pepper and spinach. The method was further applied to examine uptake of PPCPs by iceberg lettuce and spinach grown in hydroponic solutions containing each PPCP at 500 ng L⁻¹. Twelve PPCPs were detected in lettuce leaves with concentrations from 0.2 to 28.7 ng g⁻¹ dw, while 11 PPCPs were detected in spinach leaves at 0.04-34.0 ng g⁻¹ dw. Given the diverse chemical structures of PPCPs considered in this study, this method may be used for screening PPCP residues in vegetables and other plants impacted by treated wastewater or biosolids, and to estimate potential human exposure via dietary uptake. PMID:22867843

  7. Signal processing to evaluate parameters affecting SPE for multi-residue analysis of personal care products.

    PubMed

    Pietrogrande, Maria Chiara; Basaglia, Giulia; Dondi, Francesco

    2009-05-01

    This paper discusses the development of a comprehensive method for the simultaneous analysis of personal care products (PCPs) based on SPE and GC-MS. The method was developed on 29 target compounds to represent PCPs belonging to different chemical classes: surfactants in detergents (alkyl benzenes), fragrances in cosmetics (nitro and polycyclic musks), antioxidants and preservatives (phenols), plasticizers (phthalates) displaying a wide range of volatility, polarity, water solubility. In addition to the conventional C(18) stationary phase, a surface modified styrene divinylbenzene polymeric phase (Strata X SPE cartridge) has been investigated as suitable for the simultaneous extraction of several PCPs with polar and non-polar characteristics. For both sorbents different solvent compositions and eluting conditions were tested and compared in order to achieve high extraction efficiency for as many sample components as possible. Comparison of the behavior of the two cartridges reveals that, overall, Strata-X provides better efficiency with extraction recovery higher than 70% for most of the PCPs investigated. The best results were obtained under the following operative conditions: an evaporation temperature of 40 degrees C, elution on Strata-X cartridge using a volume of 15 mL of ethyl acetate (EA) as solvent and operating with slow flow rate (-10 KPa). In addition to the conventional method based on peak integration, a chemometric approach based on the computation of the experimental autocovariance function (EACVF(tot)) was applied to the complex GC-MS signal: the percentage recovery and information on peak abundance distribution can be evaluated for each procedure step. The PC-based signal processing proved very helpful in assisting the development of the analytical procedure, since it saves labor and time and increases result reliability in handling GC complex signals. PMID:19399858

  8. Determination of multi-residue insecticides of organochlorine, organophosphorus, and pyrethroids in wheat.

    PubMed

    Riazuddin; Khan, Muhammad Farhanullah; Iqbal, Sajid; Abbas, Muhammad

    2011-09-01

    The undesirable effects of green revolution include residues of extensively used pesticides in various food commodities. Several studies showed that pesticides could cause health problems. Keeping in view the problem of pesticide residues in various food commodities, the present study was conducted on domestic stored wheat as well as on imported wheat for the qualitative and quantitative analysis of organochlorine, organophosphorus and pyrethroids. Among the imported wheat, 22.5% samples were found contaminated by organophosphorus (chlorpyrifos 0.073-0.230 μg/g, malathion 0.0419-0.1003 μg/g) and pyrethroids (cypermethrin 0.1404-0.2005 μg/g, permethrin 0.0140-0.0480 μg/g) while in domestic wheat 6.7% samples were found contaminated by pyrethroids (deltamethrin 0.0650-1.2903 μg/g) only. Method used for extraction and analysis of insecticides was validated both by recovery studies and inter laboratory comparison proficiency test. The method recovery results show that the average recovery of the fortified wheat samples was in the range of 73.77%-100.17% with the RSD in the range of 2.21-9.27 whereas, the Z-scores of the inter laboratory comparison proficiency test's result was less than 2. PMID:21656043

  9. Synthesis and Biological Investigation of some Novel Sulfonamide and Amide Derivatives Containing Coumarin Moieties

    PubMed Central

    Saeedi, Mina; Goli, Fereshteh; Mahdavi, Mohammad; Dehghan, Gholamreza; Faramarzi, Mohammad Ali; Foroumadi, Alireza; Shafiee, Abbas

    2014-01-01

    New sulfonamide and amide derivatives containing coumarin moieties; oxo-2H-chromen-sulfamoylphenylacetamides and oxo-2H-chromen-arylacetamides were synthesized starting from diverse 2-chloroacetamide derivatives and a wide range of coumarins. The structures of compounds were elucidated by IR and NMR spectra and also analytical elemental analysis. In the next step, the above mentioned compounds were screened for their antimicrobial and antioxidant activities. Their antimicrobial activity was assigned using the conventional agar dilution method and the antioxidant activity was assessed using two methods, 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging method and ferric reducing antioxidant power (FRAP) assay. Although the compounds showed no remarkable antimicrobial activities, most of them exhibited good antioxidant activities. Compounds 5b showed the most potent DPPH activity, whereas 8c was the most efficient compound in FRAP assay. PMID:25276188

  10. Synthesis and Biological Investigation of some Novel Sulfonamide and Amide Derivatives Containing Coumarin Moieties.

    PubMed

    Saeedi, Mina; Goli, Fereshteh; Mahdavi, Mohammad; Dehghan, Gholamreza; Faramarzi, Mohammad Ali; Foroumadi, Alireza; Shafiee, Abbas

    2014-01-01

    New sulfonamide and amide derivatives containing coumarin moieties; oxo-2H-chromen-sulfamoylphenylacetamides and oxo-2H-chromen-arylacetamides were synthesized starting from diverse 2-chloroacetamide derivatives and a wide range of coumarins. The structures of compounds were elucidated by IR and NMR spectra and also analytical elemental analysis. In the next step, the above mentioned compounds were screened for their antimicrobial and antioxidant activities. Their antimicrobial activity was assigned using the conventional agar dilution method and the antioxidant activity was assessed using two methods, 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging method and ferric reducing antioxidant power (FRAP) assay. Although the compounds showed no remarkable antimicrobial activities, most of them exhibited good antioxidant activities. Compounds 5b showed the most potent DPPH activity, whereas 8c was the most efficient compound in FRAP assay. PMID:25276188

  11. Adamantane derivatives of sulfonamides: sublimation, solubility, solvation and transfer processes in biologically relevant solvents.

    PubMed

    Perlovich, G L; Volkova, T V; Sharapova, A V; Kazachenko, V P; Strakhova, N N; Proshin, A N

    2016-04-01

    Eight adamantane derivatives of sulfonamides were synthesized and characterized. Temperature dependencies of saturation vapor pressure were obtained using the transpiration method and thermodynamic functions of the sublimation processes were calculated. Solubility values of the selected compounds in buffer (pH 7.4), 1-octanol and 1-hexane were determined at different temperatures using the isothermal saturation method. Thermophysical characteristics of fusion processes (melting points and fusion enthalpies) of the substances were studied using the DSC method. Transfer processes from buffer to 1-octanol, from buffer to 1-hexane and 1-hexane to 1-octanol were analyzed. The impact of the molecules' structural modification on sublimation, solubility and solvation/hydration processes in the solvents was studied. Correlation equations connecting the thermodynamic functions with physicochemical descriptors were obtained. PMID:26976747

  12. Synthesis, antioxidant, enzyme inhibition and DNA binding studies of novel N-benzylated derivatives of sulfonamide

    NASA Astrophysics Data System (ADS)

    Abbas, Aadil; Murtaza, Shahzad; Tahir, Muhammad Nawaz; Shamim, Saima; Sirajuddin, Muhammad; Rana, Usman Ali; Naseem, Khadija; Rafique, Hummera

    2016-08-01

    A series of novel N-benzylated derivatives of sulfonamide were synthesized and characterized by FT-IR, NMR and XRD analysis. The synthesized compounds were assayed for their biological potential. The biological studies involved antioxidant, enzyme inhibition, and DNA interaction studies. Antioxidant potential was investigated by Ferric Reducing Antioxidant Power assay (FRAP) and DPPH free radical scavenging method, the capacity of synthesized compounds to inhibit the enzyme's activity was assayed by using the well-known Elman method whereas DNA interaction studies were carried out with the help UV-Vis absorption titration method. Moreover, a direct correlation between enzyme inhibition activity and concentration of the compounds was observed both in experimental and molecular docking studies. DNA interaction studies of the synthesized compounds showed weak interaction.

  13. A new manganese-mediated, cobalt-catalyzed three-component synthesis of (diarylmethyl)sulfonamides

    PubMed Central

    Pignon, Antoine; Martens, Thierry

    2014-01-01

    Summary The synthesis of (diarylmethyl)sulfonamides and related compounds by a new manganese-mediated, cobalt-catalyzed three-component reaction between sulfonamides, carbonyl compounds and organic bromides is described. This organometallic Mannich-like process allows the formation of the coupling products within minutes at room temperature. A possible mechanism, emphasizing the crucial role of manganese is proposed. PMID:24605162

  14. A general iodine-mediated synthesis of primary sulfonamides from thiols and aqueous ammonia.

    PubMed

    Feng, Jian-Bo; Wu, Xiao-Feng

    2016-08-01

    A general and efficient methodology for preparing primary sulfonamides has been developed. In the presence of iodine as the catalyst and TBHP (70% in water) as the oxidant, a wide range of primary sulfonamides were prepared from the corresponding thiols and aqueous ammonia in moderate to good yields. PMID:27375278

  15. Investigation of preconcentration strategies for the trace analysis of multi-residue pesticides in real samples by capillary electrophoresis.

    PubMed

    da Silva, Clóvis L; de Lima, Elizabete C; Tavares, Marina F M

    2003-10-01

    In this work, on-line preconcentration strategies were investigated for the multi-residue analysis of pesticides in drinking water and vegetables using micellar electrokinetic chromatography. Among the on-line strategies, sweeping and stacking with reverse migration of micelles (SRMM), with and without the insertion of a plug of water before sample injection, were contrasted. A new version of SRMM was also introduced. The modification consisted of momentarily applying a positive voltage at the inlet vial right after sample has been injected, increasing the efficiency by which the analytes are captured. Nine pesticides from different classes, carbendazim (benzimidazole), simazine, atrazine, propazine and ametryn (triazine), diuron and linuron (urea), carbaryl and propoxur (carbamate), were baseline separated in less than 6 min with a electrolyte composed of 20 mmol l(-1) phosphate buffer at pH 2.5, containing 25 mmol l(-1) sodium dodecyl sulfate and 10% methanol. Limits of detection (LODs) in the order of 2-46 microg l(-1) for the pesticides under investigation were obtained solely using the on-line strategies. Enrichment factors of 3-18-fold were obtained. These factors were computed as the improvement of the concentration LODs with respect to the reference condition (injection of 10 s at 2.5 kPa pressure). The proposed methodologies were applied to the analysis of pesticides in complex matrices such as carrot extracts where the detection of 2.5 microg l(-1) was illustrated. By combining off-line solid-phase extraction and the proposed on-line strategies, the detection of pesticides in drinking water at the 0.1 microg l(-1) level was conceived. PMID:14558617

  16. Carbonic Anhydrase Inhibitors. Part 541: Metal Complexes of Heterocyclic Sulfonamides: A New Class of Antiglaucoma Agents

    PubMed Central

    Scozzafava, Andrea; Jitianu, Andrei

    1997-01-01

    Metal complexes of heterocyclic sulfonamides possessing carbonic anhydrase (CA) inhibitory properties were recently shown to be useful as intraocular pressure (IOP) lowering agents in experimental animals, and might be developed as a novel class of antiglaucoma drugs. Here we report the synthesis of a heterocyclic sulfonamide CA inhibitor and of the metal complexes containing main group metal ions, such as Be(II), Mg(II), Al(III), Zn(II), Cd(II) and Hg(II) and the new sulfonamide as well as 5-amino-1,3,4-thiadiazole-2-sulfonamide as ligands. The new complexes were characterized by standard physico-chemical procedures, and assayed as inhibitors of three CA isozymes, CA I, II and IV. Some of them (but not the parent sulfonamides) strongly lowered IOP in rabbits when administered as a 2% solution into the eye. PMID:18475811

  17. Examination of intrinsic sulfonamide resistance in Bacillus anthracis: a novel assay for dihydropteroate synthase.

    PubMed

    Valderas, Michelle Wright; Andi, Babak; Barrow, William W; Cook, Paul F

    2008-05-01

    Dihydropteroate synthase (DHPS) catalyzes the formation of dihydropteroate and Mg-pyrophosphate from 6-hydroxymethyl-7,8-dihydropterin diphosphate and para-aminobenzoic acid. The Bacillus anthracis DHPS is intrinsically resistant to sulfonamides. However, using a radioassay that monitors the dihydropteroate product, the enzyme was inhibited by the same sulfonamides. A continuous spectrophotometric assay for measuring the enzymatic activity of DHPS was developed and used to examine the effects of sulfonamides on the enzyme. The new assay couples the production of MgPPi to the pyrophosphate-dependent phosphofructokinase/aldolase/triose isomerase/alpha-glycerophosphate dehydrogenase reactions and monitors the disappearance of NADH at 340nm. The coupled enzyme assay demonstrates that resistance of the B. anthracis DHPS results in part from the use of the sulfonamides as alternative substrates, resulting in the formation of sulfonamide-pterin adducts, and not necessarily due to an inability to bind them. PMID:18342015

  18. [Interaction Between Sulfonamide Antibiotics Fates and Chicken Manure Composting].

    PubMed

    Lin, Hui; Wang, Jian-mei; Sun, Wan-chun; Fu, Jian-rong; Chen, Hong-jin; Ma, Jun-wei

    2016-05-15

    Based on aerobic manure composting with or without the addition of a mixture of sulfadimethoxine SM2 and sulfamonomethoxine SMM (1:1, m/m), changes in the physic-chemical properties of manure compost, the microbial community physiological profiles, the antibiotics concentration and the abundances of five antibiotic resistance genes (ARGs) during the composting were tracked. The results indicated that the introduction of sulfonamide antibiotics led to inhibition on the basal respiration of manure compost during the early composting period, delayed the formation of thermophilic temperature and reduced the conversion of nutrients such as organic matter, ammonia nitrogen and nitrate nitrogen. Meanwhile, the introduction of sulfonamide antibiotics dramatically affected the physiological profile of microbial community in manure in the middle stage of composting. HPLC-MS/MS results showed that both SMM and SM2 in manure were completely degraded within 14 days, while the degradation rate of SMM was faster than that of SM2. For both composting treatments with or without addition of exogenous antibiotics, the relative abundance of sull and sul2 showed an initial decline in the first 14 or 21 days and a slight increase thereafter. The addition of exogenous antibiotics showed insignificant enhancement on increasing the relative abundance of sul1 and IntI1 in manure, but resulted in an apparent increase in sul2 relative abundance. Although the fates of tetQ and tetW during composting were different from that of sulfonamide ARGs, the introduction of sulfonamide antibiotics into manure increased the relative abundance of tetracycline ARGs. Redundancy analysis indicated that composting temperature correlated negatively with sul1, sul2 and IntI1 relative abundance in manure but had no obvious relationship with tetQ and tetW relative abundance. All the ARGs detected in this work correlated negatively with C/N ratio and the nitrate nitrogen concentration of manure compost but

  19. In vitro susceptibility testing of Paracoccidioides brasiliensis to sulfonamides.

    PubMed Central

    Restrepo, A; Arango, M D

    1980-01-01

    A total of 60 clinical isolates of Paracoccidioides brasiliensis were tested for susceptibility to sulfadiazine and sulfadimethoxyne by the agar dilution technique. A modification of the Mueller-Hinton medium was devised which gave good growth of the yeast form. The minimum inhibitory concentrations for only 51.6% of the isolates were in the range of the recommended blood serum concentration (50 micrograms/ml). For 6 to 8% of the isolates, the minimum inhibitory concentrations were above 200 micrograms of both sulfadiazine and sulfadimethoxyne per ml. A significant decreases in susceptibility was demonstrated for one isolate obtained from a patient relapsing during sulfonamide therapy. Images PMID:7416744

  20. Combining Organometallic Reagents, the Sulfur Dioxide Surrogate DABSO, and Amines: A One-Pot Preparation of Sulfonamides, Amenable to Array Synthesis**

    PubMed Central

    Deeming, Alex S; Russell, Claire J; Willis, Michael C

    2015-01-01

    We describe a method for the synthesis of sulfonamides through the combination of an organometallic reagent, a sulfur dioxide equivalent, and an aqueous solution of an amine under oxidative conditions (bleach). This simple reaction protocol avoids the need to employ sulfonyl chloride substrates, thus removing the limitation imposed by the commercial availability of these reagents. The resultant method allows access to new chemical space, and is also tolerant of the polar functional groups needed to impart favorable physiochemical properties required for medicinal chemistry and agrochemistry. The developed chemistry is employed in the synthesis of a targeted 70 compound array, prepared using automated methods. The array achieved a 93 % success rate for compounds prepared. Calculated molecular weights, lipophilicities, and polar surface areas are presented, demonstrating the utility of the method for delivering sulfonamides with drug-like properties. PMID:25431118

  1. Combining organometallic reagents, the sulfur dioxide surrogate DABSO, and amines: a one-pot preparation of sulfonamides, amenable to array synthesis.

    PubMed

    Deeming, Alex S; Russell, Claire J; Willis, Michael C

    2015-01-19

    We describe a method for the synthesis of sulfonamides through the combination of an organometallic reagent, a sulfur dioxide equivalent, and an aqueous solution of an amine under oxidative conditions (bleach). This simple reaction protocol avoids the need to employ sulfonyl chloride substrates, thus removing the limitation imposed by the commercial availability of these reagents. The resultant method allows access to new chemical space, and is also tolerant of the polar functional groups needed to impart favorable physiochemical properties required for medicinal chemistry and agrochemistry. The developed chemistry is employed in the synthesis of a targeted 70 compound array, prepared using automated methods. The array achieved a 93% success rate for compounds prepared. Calculated molecular weights, lipophilicities, and polar surface areas are presented, demonstrating the utility of the method for delivering sulfonamides with drug-like properties. PMID:25431118

  2. [Synthesis and bioactivities of novel dihydroartemisinin-piperazine derivatives containing sulfonamide].

    PubMed

    Ma, Chao; Li, Xue-qiang; Xu, Jian; Chen, Cou-xi

    2013-09-01

    Dihydroartemisinin is an important derivative of artemisinin. We used dihydroartemisinin as the starting material, through esterification, amination and acylation, a series of novel piperazine-sulfonamide contained dihydroartemisinin derivatives were firstly synthesized and their chemical structures were confirmed by IR, 1H NMR, 13C NMR and HR-MS. X-diffraction was used to determine the final configuration of the compound 3c. And the in vitro anti-HeLa activities of compounds 3 were analyzed with CCK-8 method. The preliminary bioassay test shows that compound 3 showed the best inhibition activities against HeLa with IC50 values of 0.14 micromol x L(-1). PMID:24358777

  3. Stereoconvergent Arylations and Alkenylations of Unactivated Alkyl Electrophiles: Catalytic Enantioselective Synthesis of Secondary Sulfonamides and Sulfones

    PubMed Central

    2015-01-01

    The development of efficient methods for the generation of enantioenriched sulfonamides and sulfones is an important objective for fields such as organic synthesis and medicinal chemistry; however, there have been relatively few reports of direct catalytic asymmetric approaches to controlling the stereochemistry of the sulfur-bearing carbon of such targets. In this report, we describe nickel-catalyzed stereoconvergent Negishi arylations and alkenylations of racemic α-bromosulfonamides and -sulfones that furnish the desired cross-coupling product in very good ee and yield for an array of reaction partners. Mechanistic studies are consistent with the generation of a radical intermediate that has a sufficient lifetime to diffuse out of the solvent cage and to cyclize onto a pendant olefin. PMID:25127186

  4. Analytical approaches to the OH radical induced degradation of sulfonamide antibiotics in dilute aqueous solutions.

    PubMed

    Sági, Gyuri; Csay, Tamás; Szabó, László; Pátzay, György; Csonka, Emil; Takács, Erzsébet; Wojnárovits, László

    2015-03-15

    By combining a large variety of analytical techniques this study aimed at elaborating methods to follow up the degradation of sulfonamides in an advanced oxidation process (AOP): irradiation with ionizing radiation in dilute aqueous solution. In this process, besides other radicals, hydroxyl radicals are produced. As pulse radiolysis experiments show the basic initial reaction is hydroxyl radical addition to the benzene ring, forming cyclohexadienyl radical intermediates. In aerated solutions these radicals transform to peroxy radicals. Among the first formed products aromatic molecules hydroxylated in the benzene rings or in some cases in the heterocyclic rings were observed by LC-MS/MS. Chemical oxygen demand (COD) measurements indicate that at the early reaction period of degradation one hydroxyl radical induces incorporation of 1.5 O atoms into the products. Comparison of the COD and TOC (total organic carbon content) results shows gradual oxidation. Simultaneously with hydroxylation ring opening also takes place. The kinetics of inorganic SO4(2-) and NH4(+) formation, analyzed by ion chromatography, is similar to the kinetics of ring degradation (UV spectroscopy), however, there is a delayed formation of NO3(-). The latter ions may be produced in oxidative degradation of smaller N containing fragments. The S atoms of the sulfonamides remain in the solution (ICP-MS measurements) after degradation, whereas some part of the N atoms leaves the solution probably in the form of N2 (total nitrogen content (TN) measurements). Degradation is accompanied by a high pH drop due to formation of SO4(2-), NO3(-) and smaller organic acids. The degradation goes through many simultaneous and consecutive reactions, and with the applied methods the different stages of degradation can be characterized. PMID:25266558

  5. Planar solid phase extraction clean-up and microliter-flow injection analysis-time-of-flight mass spectrometry for multi-residue screening of pesticides in food.

    PubMed

    Oellig, Claudia; Schwack, Wolfgang

    2014-07-18

    For multi-residue analysis of pesticides in food, a sufficient clean-up is essential for avoiding matrix effects in liquid and gas chromatography (LC and GC) analysis coupled to mass spectrometry (MS). In the last two years, high-throughput planar solid phase extraction (HTpSPE) was established as a new clean-up concept for pesticide residue analysis in fruits and vegetables (C. Oellig, W. Schwack, 2011) and tea (C. Oellig, W. Schwack, 2012). HTpSPE results in matrix-free extracts almost free of interferences and matrix effects. In this study, a time-of-flight mass spectrometer (TOFMS) was applied to directly analyze HTpSPE extracts for pesticide residues. This HTpSPE-microliter-flow injection analysis (μL-FIA)-TOFMS approach detects all pesticides at once in a single mass spectrum, without a liquid chromatographic separation step. Complete sample information was obtained after the injection of the cleaned extract within a single peak. Recovery studies for seven representative pesticides in four different matrices (apples, red grapes, cucumbers, tomatoes) provided mean recoveries of 86-116% with relative standard deviations of 1.3-10% (n=5) using the mass signal intensities under the entire sample peak. Comparing the mass spectra of sample peaks from spiked extracts and solvent standards indicated the efficiency of HTpSPE clean-up. A pesticide database search detected all spiked pesticides with a low incidence of false-positives. HTpSPE of one sample required a few minutes, and numerous samples could be cleaned in parallel at minimal cost with low sample and solvent consumption. The μL-FIA-TOFMS screening then needed an additional 6min per sample. The novel screening approach was successfully applied to QuEChERS extracts of several real samples, and the pesticides identified by HTpSPE-μL-FIA-TOFMS were identical to the pesticides detected by common target LC-MS/MS analyses. The high degree of concordantly identified pesticides by the new developed HTp

  6. Stability of sulfonamides, nitrofurans, and chloramphenicol residues in preserved raw milk samples measured by liquid chromatography.

    PubMed

    Noa, Mario; Perez, Norima; Gutierrez, Rey; Escobar, Irma; Diaz, Gilberto; Vega, Salvador; Prado, Guadalupe; Urban, Georgina

    2002-01-01

    A stability study was made of 10 antimicrobials: 6 sulfonamides, 3 nitrofurans, and chloramphenicol residues in raw milk samples preserved with 0.1 % potassium dichromate (K2Cr2O7) and 0.05% mercuric bichloride (HgCl2) during cold storage for 7 days. Preserved milk samples fortified with 50 ppb of each antimicrobial were analyzed by liquid chromatography (modified AOAC Method 993.32). Drugs were extracted with chloroform-acetone after solvent evaporation residues were dissolved with aqueous sodium acetate buffer solution (0.02M, pH 4.8), and fat was removed with hexane. Sulfonamides and chloramphenicol were detected at 275 nm (UV) by using a gradient system of sodium acetate buffer solution-acetonitrile starting at 95 + 5 (v/v) and finishing at 80 + 20 (v/v). Nitrofurans were detected at 375 nm (UV) isocratically with sodium acetate buffer solution-acetonitrile (80 + 20, v/v). Residues stability was measured through recovery data. Sulfamethoxazole, sulfachloropyridazine, nitrofurazone, furazolidone, and furaltadone residues remained stable in the presence of either preservative for 7 days. Sulfamethazine and chloramphenicol were not affected by K2Cr2O7, but had significant losses (p <0.05) when HgCl2 was used: 26.2 and 13.4%, respectively. Average recoveries of sulfamonomethoxine, sulfamerazine, and sulfathiazole significantly decreased by Day 7, with losses of 17.1, 17.2, and 23.2% for K2Cr2O7, and 23.3, 20.7, and 48.0% for HgCl2, respectively. During 5 days of cold storage all antimicrobials tested, except sulfathiazole, remained stable in milk samples preserved with 0.1 % K2Cr2O7 or 0.05% HgCl2. PMID:12477207

  7. Host-guest interaction between 3,4-dihydroisoquinoline-2(1H)-sulfonamide and β-cyclodextrin: Spectroscopic and molecular modeling studies

    NASA Astrophysics Data System (ADS)

    Seridi, Saida; Seridi, Achour; Berredjem, Malika; Kadri, Mekki

    2013-11-01

    The inclusion complex of 3,4-dihydroisoquinoline-2(1H)-sulfonamide with β-cyclodextrin was investigated experimentally and by molecular modeling studies. The stoichiometric ratio of the complex was found to be 1:1 and the stability constant was evaluated using the Benesi-Hildebrand equation. Estimation of the thermodynamic parameters of the inclusion complex in vacuum showed that it is an enthalpy driven process phase and an enthalpy-entropy co-driven process in aqueous solution, which is in accord with the experimental results. Semi-empirical calculations using PM3, PM6 and ONIOM2 methods, in vacuum and in water, were performed. The energetically more favorable structure obtained with the ONIOM2 method leads to the formation of intermolecular hydrogen bonds between sulfonamide and β-cyclodextrin. These interactions were investigated using the Natural Bond Orbital (NBO).

  8. Determination of six sulfonamide antibiotics, two metabolites and trimethoprim in wastewater by isotope dilution liquid chromatography/tandem mass spectrometry.

    PubMed

    Le-Minh, Nhat; Stuetz, Richard M; Khan, Stuart J

    2012-01-30

    A highly sensitive method for the analysis of six sulfonamide antibiotics (sulfadiazine, sulfathiazole, sulfapyridine, sulfamerazine, sulfamethazine and sulfamethoxazole), two sulfonamide metabolites (N(4)-acetyl sulfamethazine and N(4)-acetyl sulfamethoxazole) and the commonly co-applied antibiotic trimethoprim was developed for the analysis of complex wastewater samples. The method involves solid phase extraction of filtered wastewater samples followed by liquid chromatography-tandem mass spectral detection. Method detection limits were shown to be matrix-dependent but ranged between 0.2 and 0.4 ng/mL for ultrapure water, 0.4 and 0.7 ng/mL for tap water, 1.4 and 5.9 ng/mL for a laboratory-scale membrane bioreactor (MBR) mixed liquor, 0.7 and 1.7 ng/mL for biologically treated effluent and 0.5 and 1.5 ng/g dry weight for MBR activated sludge. An investigation of analytical matrix effects was undertaken, demonstrating the significant and largely unpredictable nature of signal suppression observed for variably complex matrices compared to an ultrapure water matrix. The results demonstrate the importance of accounting for such matrix effects for accurate quantitation, as done in the presented method by isotope dilution. Comprehensive validation of calibration linearity, reproducibility, extraction recovery, limits of detection and quantification are also presented. Finally, wastewater samples from a variety of treatment stages in a full-scale wastewater treatment plant were analysed to illustrate the effectiveness of the method. PMID:22284510

  9. Highly sensitive simultaneous determination of sulfonamide antibiotics and one metabolite in environmental waters by liquid chromatography-quadrupole linear ion trap-mass spectrometry.

    PubMed

    Díaz-Cruz, M Silvia; García-Galán, M Jesús; Barceló, Damià

    2008-06-01

    The present work describes the development of a highly sensitive analytical method based on liquid chromatography-quadrupole linear ion trap-mass spectrometry (LC-QqLIT-MS) for the determination of nine sulfonamide antibiotics and one N4-acetylated metabolite in environmental waters (wastewater, surface water and groundwater) and bottled mineral water. Special emphasis was devoted to the elimination of matrix components during solid-phase extraction (SPE) by the evaluation of three different extraction/purification strategies: single cartridges (Oasis HLB and Oasis MCX) and tandem (TD) extraction (combination of both). The method developed proved to be suitable for sulfonamide determination in all kinds of waters tested. The method was shown to be linear in a wide concentration range, with correlation coefficients higher than 0.999 for all compounds except for sulfadimethoxine (R2 0.997). The overall instrumental repeatability was satisfactory, with the exception of the metabolite (RSD 34%). Method limits of detection achieved for sulfonamides were in the range 0.01-1.13 ng L(-1) and for the metabolite 0.08-461 ng L(-1). Recovery rates were estimated at 500 ng L(-1) spike level in the four water matrices selected. The highest recovery achieved in all matrices was that corresponding to the Oasis HLB cartridge. In environmental waters, recovery values obtained were higher than 61% for the surface water and, in general, higher than 90% for groundwater and wastewater. Bottled mineral water exhibited recovery rates higher than 92%, with the exception of sulfamethoxypiridazine (82%) and sulfapyridine (86%) In order to demonstrate the applicability of the developed method, several water samples were analyzed. Results evidenced the requirement for consideration of N4-acetylated metabolites of sulfonamides in environmental residue analysis to avoid the underestimation of removal rates of such pharmaceutical compounds during wastewater treatments. PMID:18440009

  10. On-line solid phase extraction-ultra high performance liquid chromatography-tandem mass spectrometry as a powerful technique for the determination of sulfonamide residues in soils.

    PubMed

    Tetzner, Natália Fernanda; Maniero, Milena Guedes; Rodrigues-Silva, Caio; Rath, Susanne

    2016-06-24

    Sulfonamides are antimicrobials used widely as veterinary drugs, and their residues have been detected in environmental matrices. An analytical method for determining sulfadiazine, sulfathiazole, sulfamethazine, sulfamethoxazole, sulfadimethoxine and sulfaquinoxaline residues in soils employing a solid phase extraction on-line technique coupled with ultra-high performance liquid chromatography and tandem mass spectrometry (SPE-UHPLC-MS/MS) was developed and validated in this study. SPE and chromatographic separation were performed using an Oasis HLB column and an Acquity UPLC BEH C18 analytical column, respectively, at 40°C. Samples were prepared by extracting sulfonamides from soil using a solid-liquid extraction method with water:acetonitrile, 1:1v/v (recovery of 70.2-99.9%). The following parameters were evaluated to optimize the on-line SPE process: sorbent type (Oasis and C8), sample volume (100-400μL), loading solvent (water and different proportions of water:methanol) and washing volume (0.19-0.66mL). The method produced linear results for all sulfonamides from 0.5 to 12.5ngg(-1) with a linearity greater than 0.99. The precision of the method was less than 15%, and the matrix effect was -27% to -87%. The accuracy was in the range of 77-112% for all sulfonamides. The limit of quantitation in the two soils (clay and sand) was 0.5ngg(-1). The SPE column allowed for the analysis of many (more than 2000) samples without decreasing the efficiency. PMID:27234844

  11. Application of liquid-liquid-liquid microextraction and high-performance liquid-chromatography for the determination of sulfonamides in water.

    PubMed

    Lin, Che-Yi; Huang, Shang-Da

    2008-03-31

    This work presents a novel liquid-liquid-liquid microextraction (LLLME) technique for the extraction of sulfonamides from aqueous systems; it combines with high-performance liquid-chromatography-ultraviolet absorbance detection (HPLC/UV). In this experiment the sulfonamides were successively extracted from a donor phase (i.e., a water sample) into several microliters of an organic phase and then from the organic phase into an acceptor phase (i.e., an aqueous extract) by LLLME. The following separation and quantitative analyses were performed using HPLC/UV with 265 nm detection. Extraction condition such as solvent identity, agitation, extraction time, acceptor phase NaOH concentration, donor phase pH, and salt addition were optimized. Relative standard deviation (RSD, 2.6-5.3%), coefficient of estimation (R2, 0.9972-0.9999), and method detection limit (MDL, 0.11-0.77 ng mL(-1)) were achieved under the selected conditions. The proposed method was successfully applied to the analyses of three practical water samples and the relative recoveries of sulfonamides from the spiked water samples were in the range of 86.2-108.7%. The proposed method also confirms microextraction to be robust to monitoring trace levels of sulfacetamide, sulfadiazine, sulfathiazole, sulfamerazine, sulfadimidine, sulfamonomethoxine, sulfamethoxazole, and sulfaquinoxaline in aqueous samples. PMID:18331856

  12. Novel indole-3-sulfonamides as potent HIV non-nucleoside reverse transcriptase inhibitors (NNRTIs)

    SciTech Connect

    Zhao, Zhijian; Wolkenberg, Scott E.; Lu, Meiqing; Munshi, Vandna; Moyer, Gregory; Feng, Meizhen; Carella, Anthony V.; Ecto, Linda T.; Gabryelski, Lori J.; Lai, Ming-Tain; Prasad, Sridar G.; Yan, Youwei; McGaughey, Georgia B.; Miller, Michael D.; Lindsley, Craig W.; Hartman, George D.; Vacca, Joseph P.; Williams, Theresa M.

    2008-09-29

    This Letter describes the design, synthesis, and biological evaluation of novel 3-indole sulfonamides as potent non-nucleoside reverse transcriptase inhibitors (NNRTIs) with balanced profiles against common HIV RT mutants K103N and Y181C.

  13. Development of indole sulfonamides as cannabinoid receptor negative allosteric modulators.

    PubMed

    Greig, Iain R; Baillie, Gemma L; Abdelrahman, Mostafa; Trembleau, Laurent; Ross, Ruth A

    2016-09-15

    Existing CB1 negative allosteric modulators (NAMs) fall into a limited range of structural classes. In spite of the theoretical potential of CB1 NAMs, published in vivo studies have generally not been able to demonstrate the expected therapeutically-relevant CB1-mediated effects. Thus, a greater range of molecular tools are required to allow definitive elucidation of the effects of CB1 allosteric modulation. In this study, we show a novel series of indole sulfonamides. Compounds 5e and 6c (ABD1075) had potencies of 4 and 3nM respectively, and showed good oral exposure and CNS penetration, making them highly versatile tools for investigating the therapeutic potential of allosteric modulation of the cannabinoid system. PMID:27542310

  14. Anti-Plasmodium falciparum activity of quinoline-sulfonamide hybrids.

    PubMed

    Pinheiro, Luiz C S; Boechat, Núbia; Ferreira, Maria de Lourdes G; Júnior, Carlos C S; Jesus, Antônio M L; Leite, Milene M M; Souza, Nicolli B; Krettli, Antoniana U

    2015-09-01

    Fifteen quinoline-sulfonamide hybrids, with a 7-chloroquinoline moiety connected by a linker group to arylsulfonamide moieties with different substituents in the 4-position were synthesized and assayed against Plasmodium falciparum. The compounds displayed high schizonticidal blood activity in vitro, with IC50 values ranging from 0.05 to 1.63 μM, in the anti-HPR2 assay against clone W2-chloroquine-resistant; ten of them showed an IC50 (ranging from 0.05 to 0.40 μM) lower than that of chloroquine and sulfadoxine. Among them, two compounds inhibited Plasmodium berghei parasitemia by 47% and 49% on day 5 after mice inoculation. The most active, in vivo, hybrid 13 is considered to be a new prototype for the development of an antimalarial drug against chloroquine-resistant parasites. PMID:26190461

  15. Modularity and three-dimensional isostructurality of novel synthons in sulfonamide-lactam cocrystals.

    PubMed

    Bolla, Geetha; Mittapalli, Sudhir; Nangia, Ashwini

    2015-07-01

    The design of novel supramolecular synthons for functional groups relevant to drugs is an essential prerequisite for applying crystal engineering in the development of novel pharmaceutical cocrystals. It has been convincingly shown over the past decade that molecular level control and modulation can influence the physicochemical properties of drug cocrystals. Whereas considerable advances have been reported on the design of cocrystals for carboxylic acids and carboxamide functional groups, the sulfonamide group, which is a cornerstone of sulfa drugs, is relatively unexplored for reproducible heterosynthon-directed crystal engineering. The occurrence of synthons and isostructurality in sulfonamide-lactam cocrystals (SO2NH2⋯CONH hydrogen bonding) is analyzed to define a strategy for amide-type GRAS (generally recognized as safe) coformers with sulfonamides. Three types of supramolecular synthons are identified for the N-H donor of sulfonamide hydrogen bonding to the C=O acceptor of amide. Synthon 1: catemer synthon C 2 (1)(4) chain motif, synthon 2: dimer-cyclic ring synthon R 2 (2)(8)R 4 (2)(8) motifs, and synthon 3: dimer-catemer synthon of R 2 (2)(8)C 1 (1)(4)D notation. These heterosynthons of the cocrystals observed in this study are compared with the N-H⋯O dimer R 2 (2)(8) ring and C(4) chain motifs of the individual sulfonamide structures. The X-ray crystal structures of sulfonamide-lactam cocrystals exhibit interesting isostructurality trends with the same synthon being present. One-dimensional, two-dimensional and three-dimensional isostructurality in crystal structures is associated with isosynthons and due to their recurrence, novel heterosynthons for sulfonamide cocrystals are added to the crystal engineer's toolkit. With the predominance of sulfa drugs in medicine, these new synthons provide rational strategies for the design of binary and potentially ternary cocrystals of sulfonamides. PMID:26175899

  16. Oxidation of Sulfonamides in Aqueous Solution by UV-TiO2-Fe(VI)

    PubMed Central

    Ma, Yan; Zhang, Kejia; Li, Cong; Zhang, Tuqiao; Gao, Naiyun

    2015-01-01

    The photocatalytic degradation of sulfonamides in aqueous TiO2 suspension under UV irradiation has been investigated using potassium ferrate as electron acceptors. The results showed that the stability of Fe(VI) is dependent on pH significantly, and the stability reduces obviously in the presence of UV-TiO2. The experiments indicated that Fe(VI) could effectively scavenge the conduction band electrons from the surface of TiO2. The photocatalytic oxidation of sulfonamides with Fe(VI) was found to be much faster than that without Fe(VI). The SD, SM, and SMX concentration was greatly reduced by 89.2%, 83.4%, and 82.0%, respectively, after 10 min with UV-TiO2-Fe(VI), comparing to 65.2%, 66.0%, and 71.9%, respectively, with Fe(VI) only in the dark and 71.3%, 72.7%, and 76.0%, respectively, with UV-TiO2. The pH value of solution significantly influenced the sulfonamides degradation in UV-TiO2-Fe(VI) system. The degradation amount of sulfonamides after 10 min was a maximum at pH 7. The intermediate products of sulfonamides oxidation by UV-TiO2-Fe(VI) were analysed by LC-HESI-MS-MS and the results suggested that a majority of sulfonamides turned into large-molecule products without complete mineralization. PMID:26347888

  17. Sorption and transport of five sulfonamide antibiotics in agricultural soil and soil-manure systems.

    PubMed

    Wang, Na; Guo, Xinyan; Xu, Jing; Hao, Lijun; Kong, Deyang; Gao, Shixiang

    2015-01-01

    Animal manure application is a main spreading route of veterinary antibiotics in soil and groundwater. The sorption and leaching behavior of five commonly used sulfonamides in five typical soil and soil/manure mixtures from China were investigated in this study. Results showed that the empirical Freundlich equation fits well the sorption behavior of selected sulfonamides (r(2) was between 0.803 and 0.999, 1/n was between 0.68 and 1.44), and pH and soil organic carbon (OC) were the key impact factors to sorption and leaching. Addition of manure was found to increase the Kd values of sulfonamides in five different soils, following the rules that the more polar substances, the more increased extent of sorption after manure amendment (5.87 times for sulfadiazine with Log Kow = -0.09, and 2.49 times for sulfamethoxazole with Log Kow = 0.89). When the simulated rainfall amount reached 300 mL (180 mm), sulfonamides have high migration potential to the groundwater, especially in the soil with low OC and high pH. However, manure amendment increased the sorption capacity of sulfonamides in the top layer, thus it might play a role in decreasing the mobility of sulfonamides in soils. The systematic study would be more significant to assess the ecological risks and suggest considering the influence of manure amendment for the environmental fate of antibiotics. PMID:25421625

  18. Oxidation of Sulfonamides in Aqueous Solution by UV-TiO2-Fe(VI).

    PubMed

    Ma, Yan; Zhang, Kejia; Li, Cong; Zhang, Tuqiao; Gao, Naiyun

    2015-01-01

    The photocatalytic degradation of sulfonamides in aqueous TiO2 suspension under UV irradiation has been investigated using potassium ferrate as electron acceptors. The results showed that the stability of Fe(VI) is dependent on pH significantly, and the stability reduces obviously in the presence of UV-TiO2. The experiments indicated that Fe(VI) could effectively scavenge the conduction band electrons from the surface of TiO2. The photocatalytic oxidation of sulfonamides with Fe(VI) was found to be much faster than that without Fe(VI). The SD, SM, and SMX concentration was greatly reduced by 89.2%, 83.4%, and 82.0%, respectively, after 10 min with UV-TiO2-Fe(VI), comparing to 65.2%, 66.0%, and 71.9%, respectively, with Fe(VI) only in the dark and 71.3%, 72.7%, and 76.0%, respectively, with UV-TiO2. The pH value of solution significantly influenced the sulfonamides degradation in UV-TiO2-Fe(VI) system. The degradation amount of sulfonamides after 10 min was a maximum at pH 7. The intermediate products of sulfonamides oxidation by UV-TiO2-Fe(VI) were analysed by LC-HESI-MS-MS and the results suggested that a majority of sulfonamides turned into large-molecule products without complete mineralization. PMID:26347888

  19. Synthesis of vinca alkaloids and related compounds. Part 84. Sulfonamide derivatives of some vinca alkaloids with cardiovascular activity.

    PubMed

    Moldvai, I; Temesvári-Major, E; Szántay, C; Tóth, G; Kárpáti, E; Szántay, C

    1997-06-01

    (+)-Vincamine (1) and (+)-vinpocetine (2) were chlorosulfonylated and the resulting sulfonyl chloride isomers (3-6) were transformed into sulfonamides (7-10). The ester group of sulfonamides was modified by selective hydrolysis and transesterification. Apovincaminol derivatives (14-16) were also prepared by reduction. In addition to the known cerebrovascular effects of the unsubstituted compounds (1,2) sulfonamides also show a significant peripheral vasodilator effect. PMID:9264244

  20. [Sulfonamide-research on human subjects in Nazi concentration camps: a critical re-evaluation of the epistemological and ethical dimension].

    PubMed

    Roelcke, Volker

    2009-01-01

    Existing scholarship on the experiments performed in concentration camps beginning in 1942 on the value of sulfonamides in treatment of wound infections, in which inmates were used as experimental subjects, maintains that not only were the experiments ethically and legally completely reprehensible and unacceptable, but that they were also bad science in the sense that they were investigating questions that had already been resolved by valid medical research. In contrast to this, the paper argues on the basis of contemporary publications that the value of sulfonamides in the treatment of wound infections, including gas gangrene infections, was not yet established, that is, that the questions pursued by the experiments had not been resolved. It also argues that regarding their "design" and methodical principles, the experiments directly followed the rationality of contemporary clinical trials and animal experiments. However, for the step from animal to the human experiment, the experimental "objects" were only in regard to their body, but not to their individuality and subjectivity regarded as "human". In a concluding section, the paper lines out some implications for an adequate historical reconstruction of medical research on humans, in particular the importance of a combined focus on the scientific rationality as well as explicit or implicit value hierarchies. Further, the article points to the potential impact of such a revised image of the sulfonamide experiments for present day debates on the ethics of medical research. PMID:19496525

  1. Chlorination and oxidation of sulfonamides by free chlorine: Identification and behaviour of reaction products by UPLC-MS/MS.

    PubMed

    Gaffney, Vanessa de Jesus; Cardoso, Vitor Vale; Benoliel, Maria João; Almeida, Cristina M M

    2016-01-15

    Sulfonamides (SAs) are one class of the most widely used antibiotics around the world and have been frequently detected in municipal wastewater and surface water in recent years. Their transformation in waste water treatment plants (WWTP) and in water treatment plants (WTP), as well as, their fate and transport in the aquatic environment are of concern. The reaction of six sulfonamides (sulfamethoxazole, sulfapyridine, sulfamethazine, sulfamerazine, sulfathiazole and sulfadiazine) with free chlorine was investigated at a laboratory scale in order to identify the main chlorination by-products. A previously validated method, liquid chromatography/mass spectrometry, was used to analyse SAs and their chlorination by-products. At room temperature, pH 6-7, reaction times of up to 2 h and an initial concentration of 2 mg/L of free chlorine, the majority of SAs suffered degradation of around 65%, with the exception of sulfamethoxazole and sulfathiazole (20%). The main reaction of SAs with free chlorine occurred in the first minute. PMID:26560639

  2. Excellent performance of copper based metal organic framework in adsorptive removal of toxic sulfonamide antibiotics from wastewater.

    PubMed

    Azhar, Muhammad Rizwan; Abid, Hussein Rasool; Sun, Hongqi; Periasamy, Vijay; Tadé, Moses O; Wang, Shaobin

    2016-09-15

    The increasing concerns on toxicity of sulfonamide antibiotics in water require a prompt action to establish efficient wastewater treatment processes for their removal. In this study, adsorptive removal of a model sulfonamide antibiotic, sulfachloropyridazine (SCP), from wastewater is presented for the first time using a metal organic framework (MOF). A high surface area and thermally stable MOF, HKUST-1, was synthesized by a facile method. Batch adsorption studies were systematically carried out using HKUST-1. The high surface area and unsaturated metal sites resulted in a significant adsorption capacity with faster kinetics. Most of the SCP was removed in 15min and the kinetic data were best fitted with the pseudo second order model. Moreover, isothermal data were best fitted with the Langmuir model. The thermodynamic results showed that the adsorption is a spontaneous and endothermic process. The adsorption capacity of HKUST-1 is 384mg/g at 298K which is the highest compared to most of the materials for the antibiotics. The high adsorption capacity is attributed mainly to π-π stacking, hydrogen bonding and electrostatic interactions. PMID:27318714

  3. Multi-residue analysis of veterinary drugs, pesticides and mycotoxins in dairy products by liquid chromatography-tandem mass spectrometry using low-temperature cleanup and solid phase extraction.

    PubMed

    Xie, Jie; Peng, Tao; Zhu, Ailing; He, Jianli; Chang, Qiaoying; Hu, Xueyan; Chen, Hui; Fan, Chunlin; Jiang, Wenxiao; Chen, Min; Li, Jiancheng; Ding, Shuangyang; Jiang, Haiyang

    2015-10-01

    A multi-class multi-residue analysis method for determination of veterinary drugs, pesticides and mycotoxins in dairy products by liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been established. These 17 classes, a total of 40 kinds of target compounds were chosen because their administration to food-producing animals is banned or regulated in China and may be potentially abused or misused. Samples were extracted with acetonitrile-ethyl acetate-acetic acid (49.5+49.5+1, v/v/v). Most of lipids in the extract were removed by low-temperature cleanup, prior to solid phase extraction on HLB cartridges. The quantification and confirmation of the 40 analytes were performed by LC-MS/MS with electro-spray ionization (ESI) interface in multiple reaction monitoring (MRM) mode. The limits of detection (LODs) and limits of quantification (LOQs) were 0.006-0.3μg/kg and 0.02-1.0μg/kg, respectively. The spiked recoveries in milk, yogurt, milk powder and cheese samples were from 67.3% to 106.9%. The repeatability and the within-laboratory reproducibility were less than 12.7% and 13.9%. Applying this method, our results revealed the presences of chloramphenicol, cimeterol, and flunixin at the concentration of 0.027-0.452μg/kg in some samples. PMID:26298066

  4. Analysis of sulfonamides in soil, sediment, and sludge based on dynamic microwave-assisted micellar extraction.

    PubMed

    Wang, Hui; Ding, Jie; Ding, Lan; Ren, Nanqi

    2016-07-01

    A green and high-throughput analytical method was described for the simultaneous determination of ten sulfonamides (SAs) from soil, sediment, and sludge in northeast China. None of potentially hazardous organic solvents was used in the whole sample preparation procedure, and the total preparation time of 15 samples was about 18 min. The limits of detection for the SAs were in the range of 0.42-0.68 ng g(-1). The intra-day and inter-day precisions, expressed by the relative standard deviation, were below 7 %. Under the optimum conditions, the recoveries of ten SAs were between 69.7 and 102.7 %. The proposed method was successfully applied to analyze the SAs residues in agricultural soils, river sediments, and sewage sludge. SAs were found at the levels of 1.40-2.31 ng g(-1) and 3.77-29.29 ng g(-1) in the sediments and sludge, respectively. The aging effect of spiked soil samples on the SAs recoveries was examined, and the results demonstrate that eight SAs could persist in five soils for 3 months. Compared with the traditional method, the proposed method could reduce the consumption of the organic solvent, shorten the sample preparation time, and increase the sample throughput. PMID:26996907

  5. Ionic liquid-based aqueous two-phase system extraction of sulfonamides in milk.

    PubMed

    Shao, Mingyuan; Zhang, Xuli; Li, Na; Shi, Jiayuan; Zhang, Huijie; Wang, Zhibing; Zhang, Hanqi; Yu, Aimin; Yu, Yong

    2014-06-15

    A simple method for the determination of six sulfonamides (SAs) in milk samples was developed. 1-Butyl-3-methylimidazolium tetrafluoroborate and trisodium citrate dihydrate were used to form aqueous two-phase system. The aqueous two phase system was applied to the extraction of the SAs and the determination of the analytes was performed by high-performance liquid chromatography. To achieve optimum extraction performance, several experimental parameters, including the type and the amount of salt, the type and amount of ionic liquid, ultrasonic time and pH of sample solution, were investigated and optimized. Under the optimal experimental conditions, good linearity was observed in the range of 8.55-1036.36ngmL(-1). The limits of detection and quantification were in the range of 2.04-2.84 and 6.73-9.37ngmL(-1), respectively. The present method was successfully applied to the determination of SAs in milk samples, and the recoveries of analytes were in the range of 72.32-108.96% with relative standard deviations ranging from 0.56 to 12.20%. The results showed that the present method was rapid, feasible and environmentally friendly. PMID:24854709

  6. Crystal structures of 4-meth-oxy-N-(4-methyl-phenyl)benzene-sulfonamide and N-(4-fluoro-phenyl)-4-meth-oxy-benzene-sulfonamide.

    PubMed

    Rodrigues, Vinola Z; Preema, C P; Naveen, S; Lokanath, N K; Suchetan, P A

    2015-11-01

    Crystal structures of two N-(ar-yl)aryl-sulfonamides, namely, 4-meth-oxy-N-(4-methyl-phen-yl)benzene-sulfonamide, C14H15NO3S, (I), and N-(4-fluoro-phen-yl)-4-meth-oxy-benzene-sulfonamide, C13H12FNO3S, (II), were determined and analyzed. In (I), the benzene-sulfonamide ring is disordered over two orientations, in a 0.516 (7):0.484 (7) ratio, which are inclined to each other at 28.0 (1)°. In (I), the major component of the sulfonyl benzene ring and the aniline ring form a dihedral angle of 63.36 (19)°, while in (II), the planes of the two benzene rings form a dihedral angle of 44.26 (13)°. In the crystal structure of (I), N-H⋯O hydrogen bonds form infinite C(4) chains extended in [010], and inter-molecular C-H⋯πar-yl inter-actions link these chains into layers parallel to the ab plane. The crystal structure of (II) features N-H⋯O hydrogen bonds forming infinite one dimensional C(4) chains along [001]. Further, a pair of C-H⋯O inter-molecular inter-actions consolidate the crystal packing of (II) into a three-dimensional supra-molecular architecture. PMID:26594517

  7. Multiresidue trace analysis of sulfonamide antibiotics and their metabolites in soils and sewage sludge by pressurized liquid extraction followed by liquid chromatography-electrospray-quadrupole linear ion trap mass spectrometry.

    PubMed

    García-Galán, María Jesús; Díaz-Cruz, Silvia; Barceló, Damià

    2013-02-01

    The present study describes the development, validation and a practical application of a fully automated analytical method based on pressurized liquid extraction (PLE) followed by solid-phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) for the simultaneous determination of 22 sulfonamides, including five acetylated metabolites, in sewage sludge and soil samples. Both matrix matched calibration curves and standard calibration curves were built in order to evaluate the potential matrix effects during analysis, and different internal standards were used to compensate these effects during quantification. The recovery efficiencies were found to be 60-130% for the majority of the sulfonamides in both matrices and at two spike levels. The intra-day and inter-day precisions, expressed by the relative standard deviation (RSD), were below 23%. The method limits of detection (MLODs) achieved were in the range 0.03-2.23 ng g(-1) for sewage sludge and 0.01-4.19 ng g(-1) for soil samples. The methodology was applied to evaluate the occurrence of the target sulfonamides in several sewage sludge and soil samples taken in different wastewater treatment plants (WWTPs) and agricultural areas. Results confirmed the wide presence of sulfonamides in both matrices, being sulfathiazole and sulfamethazine the sulfonamides most frequently detected in sewage sludge and soil samples, respectively. Maximum concentrations corresponded to sulfamethazine in both cases (139.2 ng g(-1) and 8.53 ng g(-1) for sewage sludge and soils respectively). Levels were generally lower in soils. Three of the five acetylated metabolites were detected in sewage sludge and two of them in soils, at concentrations not higher than 9.81 ng g(-1). PMID:23312557

  8. Preclinical evaluation of carbon-11 and fluorine-18 sulfonamide derivatives for in vivo radiolabeling of erythrocytes

    PubMed Central

    2013-01-01

    Background To date, few PET tracers for in vivo labeling of red blood cells (RBCs) are available. In this study, we report the radiosynthesis and in vitro and in vivo evaluation of 11C and 18F sulfonamide derivatives targeting carbonic anhydrase II (CA II), a metallo-enzyme expressed in RBCs, as potential blood pool tracers. A proof-of-concept in vivo imaging study was performed to demonstrate the feasibility to assess cardiac function and volumes using electrocardiogram (ECG)-gated positron emission tomography (PET) acquisition in comparison with cine magnetic resonance imaging (cMRI) in rats and a pig model of myocardial infarction. Methods The inhibition constants (Ki) of CA II were determined in vitro for the different compounds by assaying CA-catalyzed CO2 hydration activity. Binding to human RBCs was estimated after in vitro incubation of the compounds with whole blood. Biodistribution studies were performed to evaluate tracer kinetics in NMRI mice. ECG-gated PET acquisition was performed in Wistar rats at rest and during pharmacological stress by infusing dobutamine at 10 μg/kg/min and in a pig model of myocardial infarction. Left ventricular ejection fraction (LVEF) and volumes were compared with values from cMRI. Results The Ki of the investigated compounds for human CA II was found to be in the range of 8 to 422 nM. The fraction of radioactivity associated with RBCs was found to be ≥90% at 10- and 60-min incubation of tracers with heparinized human blood at room temperature for all tracers studied. Biodistribution studies in mice indicated that 30% to 67% of the injected dose was retained in the blood pool at 60 min post injection. A rapid and sustained tracer uptake in the heart region with an average standardized uptake value of 2.5 was observed from micro-PET images. The LVEF values obtained after pharmacological stress in rats closely matched between the cMRI and micro-PET values, whereas at rest, a larger variation between LVEF values obtained by

  9. Mechanistic QSAR models for interpreting degradation rates of sulfonamides in UV-photocatalysis systems.

    PubMed

    Huang, Xiangfeng; Feng, Yi; Hu, Cui; Xiao, Xiaoyu; Yu, Daliang; Zou, Xiaoming

    2015-11-01

    Photocatalysis is one of the most effective methods for treating antibiotic wastewater. Thus, it is of great significance to determine the relationship between degradation rates and structural characteristics of antibiotics in photocatalysis processes. In the present study, the photocatalytic degradation characteristics of 10 sulfonamides (SAs) were studied using two photocatalytic systems composed of nanophase titanium dioxide (nTiO2) plus ultraviolet (UV) and nTiO2/activated carbon fiber (ACF) plus UV. The results indicated that the largest apparent SA degradation rate constant (Kapp) is approximately 5 times as large as that of the smallest one. Based on the degradation mechanism and the partial least squares regression (PLS) method, optimum Quantitative Structure Activity Relationship (QSAR) models were developed for the two systems. Mechanistic models indicated that the degradation rule of SAs in the TiO2 systems strongly relates to their highest occupied molecular orbital (Ehomo), the maximum values of nucleophilic attack (f(+)x), and the minimum values of the most negative partial charge on a main-chain atom (q(C)min), whereas the maximum values of OH radical attack (f(0)x) and the apparent adsorption rate constant values (kad) are key factors affecting the degradation rule of SAs in the TiO2/ACF system. PMID:26070083

  10. [Determination of 12 sulfonamides in cosmetics by ultra performance liquid chromatography].

    PubMed

    Zheng, Hehui; Wang, Ping; Li, Jie

    2007-03-01

    A method for the determination of 12 sulfonamides (SAs) (sulfanilamide, sulfamonomethoxine, sulfacetamide, sulfamethoxazole, sulfadiazine, sulfisoxazole, sulfathiazole, sulfadi-methoxine, sulfamerazine, sulfaquinoxaline, sulfamethazine, sulfanitran) in cosmetics was developed by ultra performance liquid chromatography with photodiode array detector (UPLC-PDA). The chromatographic column used was Acquity UPLC BEHC C18 (50 mm x 2. 1 mm, 1. 7 microm) and the mobile phase was acetonitrile-0. 1% formic acid aqueous solution. A gradient elution program was utilized for the separation and determination. After liquid-liquid extraction, SAs were separated and detected by UPLC-PDA. The qualification analysis was done by using retention time and spectrum, and the quantification was based on the detection wavelength of 268 nm. The limits of qualification (S/N = 3) and quantification (S/N = 10) for 12 SAs were 1 microg/g and 2 -3 microg/g, respectively. The correlation coefficient of linear calibration curve was over 0. 999 7 within the SAs concentration range of 1 - 25 mg/L (except sulfanitran 0. 5 - 12. 5 mg/L). At the spiked levels of 40 and 8 microg (except sulfanitran 20 and 4 microg), the average recoveries for 12 SAs were 86. 8% - 98. 1% and 80. 1% - 96. 9%, respectively. Relative standard deviations were less than 10%. Routine tests show that the method is simple, fast, and has a good separation efficiency. It can be routinely used for the determination of these SAs in cosmetics. PMID:17580695

  11. Fast and selective extraction of sulfonamides from honey based on magnetic molecularly imprinted polymer.

    PubMed

    Chen, Ligang; Zhang, Xiaopan; Sun, Lei; Xu, Yang; Zeng, Qinglei; Wang, Hui; Xu, Haoyan; Yu, Aimin; Zhang, Hanqi; Ding, Lan

    2009-11-11

    A fast and selective method was developed for the determination of sulfonamides (SAs) in honey based on magnetic molecularly imprinted polymer. The extraction was carried out by blending and stirring the sample, extraction solvent and polymers. When the extraction was complete, the polymers, along with the captured analytes, were easily separated from the sample matrix by an adscititious magnet. The analytes eluted from the polymers were determined by liquid chromatography-tandem mass spectrometry. Under the optimal conditions, the detection limits of SAs are in the range of 1.5-4.3 ng g(-1). The relative standard deviations of intra- and interday ranging from 3.7% to 7.9% and from 4.3% to 9.9% are obtained, respectively. The proposed method was successfully applied to determine SAs including sulfadiazine, sulfamerazine, sulfamethoxydiazine, sulfamonomethoxine, sulfadimethoxine, sulfamethoxazole and sulfaquinoxaline in different honey samples. The recoveries of SAs in these samples from 67.1% to 93.6% were obtained. PMID:19817457

  12. Determination of sulfonamides in soil samples based on alumina-coated magnetite nanoparticles as adsorbents.

    PubMed

    Sun, Lei; Sun, Xin; Du, Xiaobo; Yue, Yanshan; Chen, Ligang; Xu, Haoyan; Zeng, Qinglei; Wang, Hui; Ding, Lan

    2010-04-30

    In this study, alumina-coated magnetite nanoparticles (Fe(3)O(4)/Al(2)O(3) NPs) were synthesized, and they were applied to the analysis of sulfonamides (SAs) including sulfadiazine (SDZ), sulfamerazine (SMR), sulfamethoxazole (SMX), sulfamonomethoxine (SMM), sulfamethoxydiazine (SMD), sulfadimethoxine (SDM) and sulfaquinoxaline (SQX) in different soil samples based on magnetic solid-phase extraction (MSPE). The extraction and concentration process was carried out in a single step by mixing the extraction solvent, magnetic adsorbents and soil sample under ultrasonic action. Then, the adsorbents were isolated from the complicated matrix easily with an external magnetic field. The SAs desorbed from the adsorbents were determined by liquid chromatography-tandem mass spectrometry. Compared with traditional methods, the MSPE method simplified the operation procedure and reduced the analysis time. Under the optimum conditions, the recoveries of SDZ, SMR, SMX, SMM, SMD and SDM by analyzing the five spiked soil samples were between 71% and 93% except for SQX (42-60%). This may be due to the stronger hydrophobic property of SQX. Detection limits of SAs were between 0.37 and 6.74 ng g(-1). It was also found that the "aging" effect of SAs contaminated soil could cause the recoveries to decrease. PMID:20417329

  13. Design, synthesis, crystal structures and antimicrobial activity of sulfonamide boronic acids as β-lactamase inhibitors

    PubMed Central

    Eidam, Oliv; Romagnoli, Chiara; Caselli, Emilia; Babaoglu, Kerim; Pohlhaus, Denise Teotico; Karpiak, Joel; Bonnet, Richard; Shoichet, Brian K.; Prati, Fabio

    2010-01-01

    We investigated a series of sulfonamide boronic acids that resulted from the merging of two unrelated AmpC β-lactamase inhibitor series. The new boronic acids differed in the replacement of the canonical carboxamide, found in all penicillin and cephalosporin antibiotics, with a sulfonamide. Surprisingly, these sulfonamides had a highly distinct structure-activity relationship from the previously explored carboxamides, high ligand efficiencies (up to 0.91), Ki values down to 25 nM and up to 23 times better for smaller analogs. Conversely, Ki values were 10 to 20 times worse for larger molecules than in the carboxamide congener series. X-ray crystal structures (1.6–1.8 Å) of AmpC with three of the new sulfonamides suggest that this altered structure-activity relationship results from the different geometry and polarity of the sulfonamide versus the carboxamide. The most potent inhibitor reversed β-lactamase-mediated resistance to third generation cephalosporins, lowering their minimum inhibitory concentrations up to 32-fold in cell culture. PMID:20945905

  14. A non-target approach to identify disinfection byproducts of structurally similar sulfonamide antibiotics.

    PubMed

    Wang, Mian; Helbling, Damian E

    2016-10-01

    There is growing concern over the formation of new types of disinfection byproducts (DBPs) from pharmaceuticals and other emerging contaminants during drinking water production. Free chlorine is a widely used disinfectant that reacts non-selectively with organic molecules to form a variety of byproducts. In this research, we aimed to investigate the DBPs formed from three structurally similar sulfonamide antibiotics (sulfamethoxazole, sulfathiazole, and sulfadimethoxine) to determine how chemical structure influences the types of chlorination reactions observed. We conducted free chlorination experiments and developed a non-target approach to extract masses from the experimental dataset that represent the masses of candidate DBPs. Structures were assigned to the candidate DBPs based on analytical data and knowledge of chlorine chemistry. Confidence levels were assigned to each proposed structure according to conventions in the field. In total, 11, 12, and 15 DBP structures were proposed for sulfamethoxazole, sulfathiazole, and sulfadimethoxine, respectively. The structures of the products suggest a variety of reaction types including chlorine substitution, SC cleavage, SN hydrolysis, desulfonation, oxidation/hydroxylation, and conjugation reactions. Some reaction types were common to all of the sulfonamide antibiotics, but unique reaction types were also observed for each sulfonamide antibiotic suggesting that selective prediction of DBP structures of other sulfonamide antibiotics based on chemical structure is unlikely to be possible based on these data alone. This research offers an approach to comprehensively identify DBPs of organic molecules and fills in much needed data on the formation of specific DBPs from three environmentally relevant sulfonamide antibiotics. PMID:27348196

  15. Impact of selected wastewater constituents on the removal of sulfonamide antibiotics via ultrafiltration and micellar enhanced ultrafiltration.

    PubMed

    Exall, Kirsten; Balakrishnan, Vimal K; Toito, John; McFadyen, Renée

    2013-09-01

    To better understand the environmental mobility of sulfonamide antibiotics and develop improved processes for their removal during wastewater treatment, stirred cell ultrafiltration (UF) experiments were conducted using both synthetic and real wastewater effluent. The interactions between selected sulfonamides (sulfaguanidine, sulfathiazole and sulfamerazine), solids and dissolved organic matter were systematically explored. The further impact of micellar enhanced ultrafiltration (MEUF), a process in which surfactants are added at micellar concentrations to enhance removal of various trace contaminants from aqueous streams, was then explored by using a cationic surfactant, cetyltrimethylammonium bromide (CTAB). Ultrafiltration of sulfonamides in the absence of other materials generally removed only 15-20% of the antibiotics. The presence of micellar solutions of CTAB generally improved removal of sulfonamides over UF alone, with rejections ranging from 20 to 74%. Environmental solids (sediment) further increased retention of sulfonamides using both UF and MEUF, but the presence of DOM did not influence rejection. Similar trends were observed on UF and MEUF of real effluent samples that had been spiked with the sulfonamides, confirming the environmental relevance of the observed interactions between sulfonamides, surfactant, and wastewater constituents. The results demonstrate that MEUF processes can be designed for the selective removal of such trace contaminants as sulfonamide antibiotics. PMID:23743146

  16. High-performance liquid chromatographic procedure for routine residue monitoring of seven sulfonamides in milk.

    PubMed

    Furusawa, N; Kishida, K

    2001-12-01

    A simplified method for routine monitoring of 7 residual sulfonamides (SAs) (sulfadiazine (SDZ), sulfamerazine (SMR), sulfadimidine (SDD), sulfamonomethoxine (SMM), sulfamethoxazole (SMX), sulfadimethoxine (SDM), and sulfaquinoxaline (SQ)) in milk using high-performance liquid chromatography (HPLC) with a photodiode array detector is described. The spiked and blank samples were cleaned up by using an Ultrafree-MC/PL centrifugal ultrafiltration unit. For determination/identification, a Mightysil RP-4 GP column and a mobile phase of 25% (v/v) ethanol in water with a photodiode array detector were used. Average recoveries from milk samples spiked with 0.05, 0.1, 0.2, and 0.5 microg mL(-1) of each drug were >82%. The inter- and intra-assay variabilities were 2.0-3.1%. The practical detection limits for 7 SAs were 0.005-0.02 microg mL(-1). The total time and amount of solvent required for the analysis of one sample were <40 min and <6 mL of ethanol, respectively. No toxic solvents were used. PMID:11769794

  17. Evaluation of the aquatic toxicity of two veterinary sulfonamides using five test organisms.

    PubMed

    De Liguoro, Marco; Di Leva, Vincenzo; Gallina, Guglielmo; Faccio, Elisabetta; Pinto, Gabriele; Pollio, Antonino

    2010-10-01

    The aquatic toxicity of sulfaquinoxaline (SQO) and sulfaguanidine (SGD) was evaluated on the following test organisms: Daphnia magna (reproduction test), Pseudokirchneriella subcapitata, Scenedesmus dimorphus, Synecococcus leopoliensis (algal growth inhibition test) and Lemna gibba (duckweed growth inhibition test). Furthermore, the additivity of the two compounds was measured on D. magna (acute immobilisation test) and P. subcapitata (algal growth inhibition test) using the isobologram method. Results show that SQO and SGD are more toxic to green algae and daphnids, respectively, than other veterinary sulfonamides (SAs) and that their mixtures have a less then additive interaction. Taking into account the highest concentrations detected so far in surface waters for SQO (0.112 μg L(-1)) and for SGD (0.145 μg L(-1)) and the lowest NOECs obtained with the five test organisms, divided by an assessment factor of 10, the following PNECs and risk quotients (RQs) were calculated. SQO: PNEC 2 μg L(-1); RQ 0.056. SGD: PNEC 39.5 μg L(-1); RQ 0.004. Consequently, at the concentrations actually detected in the aquatic environment, the two SAs alone should not harm the freshwater organisms. However, it seems advisable, for veterinary mass treatments, the use of other SAs that have a lesser impact on the aquatic environment. Furthermore, considering the high probability of having complex mixtures of different SAs residues in water, each individual contamination should be evaluated by applying to the SAs mixtures the conservative criteria of additivity. PMID:20673955

  18. [Determination of residual sulfonamides in meat by high performance liquid chromatography with solid-phase extraction].

    PubMed

    Zhang, Yan; Wu, Yinliang

    2005-11-01

    A method was developed for determining residual sulfonamides (SAs) such as sulfamethazine (SM2), sulfamonomethoxine (SMM), sulfamethiazole (SMZ), sulfadimethoxine (SDM) and sulfaquinoxaline (SQ) in pork and chicken using solid-phase extraction (SPE) and high performance liquid chromatography (HPLC) with a photodiode array detector. The samples were extracted with ethyl acetate. An NH2 column was used for clean up. For the HPLC determination, an Intersil ODS-2 column was used with a mixture of methanol-acetonitrile-water-acetic acid (2: 2: 9: 0.2, v/v) as the mobile phase. The detection limits (S/N = 3) were 3 microg/kg for SM2, SMM and SMZ, and 7 microg/kg for SDM and SQ. The quantitation limits (S/N = 10) were 10 microg/kg for SM2, SMM and SMZ, and 25 microg/kg for SDM and SQ. The linear ranges were 30 - 5 000 microg/L for SM2, SMM and SMZ, and 60 - 5 000 microg/L for SDM and SQ. The recoveries were between 73.2% and 97.3% with the relative standard deviations between 2.5% and 11.6% originated from the spiked level of 50 microg/kg. PMID:16498995

  19. Mechanistic model for interpreting the toxic effects of sulfonamides on nitrification.

    PubMed

    Huang, Xiangfeng; Feng, Yi; Hu, Cui; Xiao, Xiaoyu; Yu, Daliang; Zou, Xiaoming

    2016-03-15

    Antibiotics are categorized as pseudopersistent compounds because of their widespread use and continuous emission into the environment. Biological systems such as active sludge and biofilms are still the principal tools used to remove antibiotics in wastewater treatment plants (WWTPs). Consequently, it is important to determine the relationship between toxic effects in biological WWTPs and the structural characteristics of antibiotics. In the present study, toxic effects of 10 sulfonamides (SAs) on nitrification in an active sludge system were studied. The toxicity results (half-effective concentrations, EC50) indicated that the toxicity of sulfadimethoxine (SDM) is approximately 4 times as large as that of sulfadiazine (SD). Based on the toxicity mechanism and the partial least squares regression (PLS) method, an optimum quantitative structure-activity relationship (QSAR) model was developed for the test system. The mechanistic model showed that the pKa, the binding energies between SAs with dihydropteroate synthetase ( [Formula: see text] ) and the binding energies between SAs with ammonia monooxygenase ( [Formula: see text] ) are the key factors affecting the toxic effects of SAs on nitration process in active sludge system, following an order of importance of [Formula: see text] > [Formula: see text] >pKa. PMID:26651069

  20. Synthesis of new carbon-11 labeled naphthalene-sulfonamides for PET imaging of human CCR8.

    PubMed

    Wang, Min; Cooley, Benjamin; Gao, Mingzhang; Miller, Kathy D; Sledge, George W; Hutchins, Gary D; Zheng, Qi-Huang

    2008-10-01

    Carbon-11 labeled naphthalene-sulfonamides, N-(4-(N-(4-[(11)C]methoxyphenyl)sulfamoyl)naphthalene-1-yl)benzamide ([(11)C]5a), N-(4-(N-(4-[(11)C]methoxyphenyl)sulfamoyl)naphthalene-1-yl)-2-methylbenzamide ([(11)C]5b), N-(4-(N-(4-[(11)C]methoxyphenyl)sulfamoyl)naphthalene-1-yl)-3-methylbenzamide ([(11)C]5c), N-[(11)C]methyl-N-methyl-4-(4-benzamidonaphthalene-1-sulfonamido)piperidine-1-carboxamide ([(11)C]9a) and N-[(11)C]methyl-N-methyl-4-(4-(2-methylbenzamido)naphthalene-1-sulfonamido)piperidine-1-carboxamide ([(11)C]9b), have been synthesized as new potential positron emission tomography (PET) agents for imaging of human CCR8. The target tracers were prepared by either O-[(11)C]methylation or N-[(11)C]methylation of their corresponding precursors using [(11)C]CH(3)OTf and isolated by either a simplified solid-phase extraction (SPE) purification procedure or a high pressure liquid chromatography (HPLC) method in 30-50% radiochemical yields decay corrected to end of bombardment (EOB), 20-25 min overall synthesis time, and 74-111 GBq/micromol specific activity at end of synthesis (EOS). PMID:18455923

  1. Assessing antibiotic sorption in soil: a literature review and new case studies on sulfonamides and macrolides

    PubMed Central

    2014-01-01

    The increased use of veterinary antibiotics in modern agriculture for therapeutic uses and growth promotion has raised concern regarding the environmental impacts of antibiotic residues in soil and water. The mobility and transport of antibiotics in the environment depends on their sorption behavior, which is typically predicted by extrapolating from an experimentally determined soil-water distribution coefficient (Kd). Accurate determination of Kd values is important in order to better predict the environmental fate of antibiotics. In this paper, we examine different analytical approaches in assessing Kd of two major classes of veterinary antibiotics (sulfonamides and macrolides) and compare the existing literature data with experimental data obtained in our laboratory. While environmental parameters such as soil pH and organic matter content are the most significant factors that affect the sorption of antibiotics in soil, it is important to consider the concentrations used, the analytical method employed, and the transformations that can occur when determining Kd values. Application of solid phase extraction and liquid chromatography/mass spectrometry can facilitate accurate determination of Kd at environmentally relevant concentrations. Because the bioavailability of antibiotics in soil depends on their sorption behavior, it is important to examine current practices in assessing their mobility in soil. PMID:24438473

  2. Synthesis and description of intermolecular interactions in new sulfonamide derivatives of tranexamic acid

    NASA Astrophysics Data System (ADS)

    Ashfaq, Muhammad; Arshad, Muhammad Nadeem; Danish, Muhammad; Asiri, Abdullah M.; Khatoon, Sadia; Mustafa, Ghulam; Zolotarev, Pavel N.; Butt, Rabia Ayub; Şahin, Onur

    2016-01-01

    Tranexamic acid (4-aminomethyl-cyclohexanecarboxylic acid) was reacted with sulfonyl chlorides to produce structurally related four sulfonamide derivatives using simple and environmental friendly method to check out their three-dimensional behavior and van der Walls interactions. The molecules were crystallized in different possibilities, as it is/after alkylation at its O and N atoms/along with a co-molecule. All molecules were crystallized in monoclinic crystal system with space group P21/n, P21/c and P21/a. X-ray studies reveal that the molecules stabilized themselves by different kinds of hydrogen bonding interactions. The molecules are getting connected through O-H⋯O hydrogen bonds to form inversion dimers which are further connected through N-H⋯O interactions. The molecules in which N and O atoms were alkylated showed non-classical interaction and generated centro-symmetric R22(24) ring motif. The co-crystallized host and guest molecules are connected to each other via O-H⋯O interactions to generate different ring motifs. By means of the ToposPro software an analysis of the topologies of underlying nets that correspond to molecular packings and hydrogen-bonded networks in structures under consideration was carried out.

  3. Ecotoxicity evaluation and removal of sulfonamides and their acetylated metabolites during conventional wastewater treatment.

    PubMed

    García-Galán, María Jesús; González Blanco, Susana; López Roldán, Ramón; Díaz-Cruz, Silvia; Barceló, Damiá

    2012-10-15

    The present study describes the evaluation of the risk posed by the occurrence of sulfonamides (SAs) in wastewaters. A fully automated analytical method based on on-line solid-phase extraction-liquid chromatography-tandem mass spectrometry (on line SPE-LC-MS/MS) was developed, validated and applied for the analysis of sixteen SAs and, for the first time in wastewaters and sewage sludge, five of their acetylated metabolites. Influent and effluent samples from twenty two different wastewater treatment plants (WWTPs) in Catalonia (Spain) and sewage sludge from fifteen of them were analyzed; removal rates (RE%) and half-lives (t(1/2)) for each SA were calculated. The estimated correlations between RE% and to the hydraulic retention time (HRT) of the different plants indicated no clear influence of HRT on removals. Sulfamethoxazole (SMX), sulfapyridine (SPY) and their corresponding acetylated metabolites were detected with the highest frequencies of detection and at the highest concentrations. The ecotoxicity of both SPY and AcSPY was evaluated for the first time through bioluminescent inhibition assays, resulting in a higher toxicity being attributed to the metabolite. Finally, the potential environmental risk posed by the levels of SAs detected was evaluated calculating the hazard quotients (HQ) to different non-target aquatic organisms in treated wastewaters. SMX was the only SA posing a risk to algae, with an HQ>10. PMID:22960452

  4. Furazan and furoxan sulfonamides are strong α-carbonic anhydrase inhibitors and potential antiglaucoma agents.

    PubMed

    Chegaev, Konstantin; Lazzarato, Loretta; Tamboli, Yasinalli; Boschi, Donatella; Blangetti, Marco; Scozzafava, Andrea; Carta, Fabrizio; Masini, Emanuela; Fruttero, Roberta; Supuran, Claudiu T; Gasco, Alberto

    2014-08-01

    A series of furazan and furoxan sulfonamides were prepared and studied for their ability to inhibit human carbonic anhydrase (CA, EC 4.2.1.1) isoforms hCA I, hCA II, hCA IX, and hCA XII. The simple methyl substituted products 3-5 were potent inhibitors. Differing structural modifications of these leads had differing effects on potency and selectivity. In particular, products in which the sulfonamide group is separated from the hetero ring by a phenylene bridge retained high potency only on the hCA XII isoform. The sulfonamides 3-5 exerted intraocular pressure (IOP) lowering effects in vivo in hypertensive rabbits more efficiently than dorzolamide. Some other products (39-42), although less effective in vitro hCA II/XII inhibitors, also effectively lowered IOP in two different animal models of glaucoma. PMID:25022971

  5. Multi-class, multi-residue analysis of pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenyl ethers and novel flame retardants in fish using fast, low-pressure gas chromatography-tandem mass spectrometry.

    PubMed

    Sapozhnikova, Yelena; Lehotay, Steven J

    2013-01-01

    A multi-class, multi-residue method for the analysis of 13 novel flame retardants, 18 representative pesticides, 14 polychlorinated biphenyl (PCB) congeners, 16 polycyclic aromatic hydrocarbons (PAHs), and 7 polybrominated diphenyl ether (PBDE) congeners in catfish muscle was developed and evaluated using fast low pressure gas chromatography triple quadrupole tandem mass spectrometry (LP-GC/MS-MS). The method was based on a QuEChERS (quick, easy, cheap, effective, rugged, safe) extraction with acetonitrile and dispersive solid-phase extraction (d-SPE) clean-up with zirconium-based sorbent prior to LP-GC/MS-MS analysis. The developed method was evaluated at 4 spiking levels and further validated by analysis of NIST Standard Reference Materials (SRMs) 1974B and 1947. Sample preparation for a batch of 10 homogenized samples took about 1h/analyst, and LP-GC/MS-MS analysis provided fast separation of multiple analytes within 9min achieving high throughput. With the use of isotopically labeled internal standards, recoveries of all but one analyte were between 70 and 120% with relative standard deviations less than 20% (n=5). The measured values for both SRMs agreed with certified/reference values (72-119% accuracy) for the majority of analytes. The detection limits were 0.1-0.5ng g(-1) for PCBs, 0.5-10ng g(-1) for PBDEs, 0.5-5ng g(-1) for select pesticides and PAHs and 1-10ng g(-1) for flame retardants. The developed method was successfully applied for analysis of catfish samples from the market. PMID:23245899

  6. Effects of pH and manure on transport of sulfonamide antibiotics in soil.

    PubMed

    Strauss, Claudia; Harter, Thomas; Radke, Michael

    2011-01-01

    Sulfonamide antibiotics are a commonly used group of compounds in animal husbandry. They are excreted with manure, which is collected in a storage lagoon in certain types of confined animal feeding operations. Flood irrigation of forage fields with this liquid manure creates the potential risk of groundwater contamination in areas with shallow groundwater levels. We tested the hypothesis that-in addition to the soil characteristics-manure as cosolute and manure pH are two major parameters influencing sulfonamide transport in soils. Solute displacement experiments in repacked, saturated soil columns were performed with soil (loamy sand) and manure from a dairy farm in California. Breakthrough of nonreactive tracer and sulfadimethoxine, sulfamethazine, and sulfamethoxazole at different solution pH (5, 6.5, 8.5) with and without manure was modeled using Hydrus-1D to infer transport and reaction parameters. Tracer and sulfonamide breakthrough curves were well explained by a model concept based on physical nonequilibrium transport, equilibrium sorption, and first-order dissipation kinetics. Sorption of the antibiotics was low ( K₄ ≤ 0.7 L kg) and only weakly influenced by pH and manure. However, sulfonamide attenuation was significantly affected by both pH and manure. The mass recovery of sulfonamides decreased with decreasing pH, e.g., for sulfamethoxazole from 77 (pH 8.5) to 56% (pH 5). The sulfonamides were highly mobile under the studied conditions, but manure application increased their attenuation substantially. The observed attenuation was most likely caused by a combination of microbial transformation and irreversible sorption to the soil matrix. PMID:21869527

  7. [Qualification and quantification of 10 sulfonamides in animal feedstuff by high performance liquid chromatography-electrospray tandem mass spectrometry].

    PubMed

    Qin, Yan; Zhang, Meijin; Lin, Haidan

    2005-07-01

    The presence of sulfonamide (SA) residues in foods is largely due to the raising of animals with sulfonamide antibiotics added or polluted feedstuff. Because of interference from the matrices, the commonly used immunoassay or chromatographic method is not suitable for the analysis of multi-SAs in feedstuff. A high performance liquid chromatographic-electrospray tandem mass spectrometric (HPLC/ESI-MS-MS) method has been established for the simultaneous determination of multi-SAs including sulfadiazine (SD), sulfapyridine (SPD), sulfamerazine (SM1), sulfameter (SM), sulfamethazine (SM2), sulfamethoxypyridazine (SMP), sulfamethoxazole (SMZ), sulfamonomethoxine (SMM), sulfadimethoxine (SDM) and sulfaquinoxaline (SQX). After solvent extraction, solid phase extraction, dilution and reversed-phase HPLC separation, SAs were detected by ESI-MS-MS under multi-reaction monitoring mode. The qualification analysis was done by using retention time and distribution of diagnostic ion pairs, and the quantification was based on the peak intensity of common fragment ion m/z 156. The limits of quantification for 10 SAs were 0.5 - 2.0 microg/kg (S/N = 10). The correlation coefficient of linear calibration curve was over 0.9995 within the SAs concentration range 2.0 - 200 microg/L except for SDM and SQX. At the spiked level of 1.0 mg/kg, the average recoveries for the 10 SAs were between 70% and 92%, the relative standard deviations were under 10% for intra-day and under 15% for inter-day. Routine tests showed the method was fast, sensitive, specific, and practical for the SAs determination in feedstuff. PMID:16250451

  8. Synthesis and biochemical evaluation of triazole/tetrazole-containing sulfonamides against thrombin and related serine proteases

    PubMed Central

    Siles, Rogelio; Kawasaki, Yuko; Ross, Patrick; Freire, Ernesto

    2011-01-01

    A small library of 25 triazole/tetrazole-based sulfonamides have been synthesized and further evaluated for their inhibitory activity against thrombin, trypsin, tryptase and chymase. In general, the triazole-based sulfonamides inhibited thrombin more efficiently than the tetrazole counterparts. Particularly, compound 26 showed strong thrombin inhibition (Ki =880 nM) and significant selectivity against other human related serine proteases like trypsin (Ki =729 µM). Thrombin binding affinity of the same compound was determined by ITC and demonstrated that the binding of this new triazole-based scaffold is enthalpically driven, making it a good candidate for further development. PMID:21807511

  9. Evaluation of novel trans-sulfonamide platinum complexes against tumor cell lines.

    PubMed

    Pérez, Carlos; Díaz-García, C Vanesa; Agudo-López, Alba; del Solar, Virginia; Cabrera, Silvia; Agulló-Ortuño, M Teresa; Navarro-Ranninger, Carmen; Alemán, José; López-Martín, José A

    2014-04-01

    Platinum-based drugs, mainly cisplatin, are employed for the treatment of solid malignancies. However, cisplatin treatment often results in the development of chemoresistance, leading to therapeutic failure. Here, the antitumor activity of different trans-sulfonamide platinum complexes in a panel of human cell lines is presented. The cytotoxicity profiles and cell cycle analyses of these platinum sulfonamide complexes were different from those of cisplatin. These studies showed that complex 2b with cyclohexyldiamine and dansyl moieties had the best antitumoral activities. PMID:24589491

  10. Multi-component analysis of tetracyclines, sulfonamides and tylosin in swine manure by liquid chromatography-tandem mass spectrometry.

    PubMed

    Jacobsen, Anne Marie; Halling-Sørensen, Bent

    2006-03-01

    A multi-component method focussing on thorough sample preparation has been developed for simultaneous analysis of swine manure for three classes of antibiotic-tetracyclines, sulfonamides, and tylosin. Liquid manure was initially freeze-dried and homogenised by pulverization before extraction by pressurised liquid extraction. The extraction was performed at 75 degrees C and 2,500 psig in three steps using two cycles with 0.2 mol L(-1) citric acid buffer (pH 4.7) and one cycle with a mixture of 80% methanol with 0.2 mol L(-1) citric acid (pH 3). After liquid-liquid extraction with heptane to remove lipids, the pH of the manure was adjusted to 3 with formic acid and the sample was vacuum-filtered through 0.6 mum glass-fibre filters. Finally the samples were pre-concentrated by tandem SPE (SAX-HLB). Recoveries were determined for manure samples spiked at three concentrations (50-5,000 microg kg(-1) dry matter); quantification was achieved by matrix-matched calibration. Recoveries were >70% except for oxytetracycline (42-54%), sulfadiazine (59-73%), and tylosin (9-35%) and did not vary with concentration or from day-to-day. Limits of quantification (LOQ) for all compounds, determined as a signal-to-noise ratio of 10, were in the range 10-100 microg kg(-1) dry matter. The suitability of the method was assessed by analysis of swine manure samples from six different pig-production sites, e.g. finishing pigs, sows, or mixed production. Residues of antibiotics were detected in all samples. The largest amounts were found for tetracyclines (up to 30 mg kg(-1) dry matter for the sum of CTC and ECTC). Sulfonamides were detected at concentrations up to 2 mg kg(-1) dry matter (SDZ); tylosin was not detected in any samples. PMID:16485090

  11. Comparative study of different chromatographic techniques for the analysis of multi-residues of some approved antimicrobials in fish tissues.

    PubMed

    Riad, Safa'a M; Rezk, Mamdouh R; Khattab, Fatma I; Marzouk, Hoda M

    2015-01-01

    Two chromatographic methods were developed, optimized and validated for the simultaneous determination of three approved aquaculture antimicrobials, namely sulphadimethoxine sodium, trimethoprim and florphenicol in fish tissues. The developed methods were based on simple liquid extraction technique. The first method employs thin-layer chromatography as a clean-up procedure coupled with densitometric determination for the separated drugs. The second method is an HPLC one using X-Terra™ C18 column. Several mobile-phase systems and extracting solvents were tried to optimize the separation and the extraction procedures from fish tissues. The procedures were applied for the analysis of spiked fish tissue samples at three different concentration levels (10, 50 and 100 ppm). A comparative study was conducted between the proposed methods to discuss the advantage of each one. The methods were validated according to the international conference on harmonization guidelines. The proposed methods were successfully applied for the determination of the studied drugs in spiked fish tissues, pure powders and in their veterinary pharmaceutical formulation. PMID:26184768

  12. 21 CFR 558.15 - Antibiotic, nitrofuran, and sulfonamide drugs in the feed of animals.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS NEW ANIMAL DRUGS FOR USE IN ANIMAL FEEDS General Provisions § 558.15 Antibiotic, nitrofuran, and sulfonamide drugs in the feed... subtherapeutic (increased rate of gain, disease prevention. etc.) uses in animal feed of antibiotic...

  13. 21 CFR 558.15 - Antibiotic, nitrofuran, and sulfonamide drugs in the feed of animals.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS NEW ANIMAL DRUGS FOR USE IN ANIMAL FEEDS General Provisions § 558.15 Antibiotic, nitrofuran, and sulfonamide drugs in the feed... subtherapeutic (increased rate of gain, disease prevention. etc.) uses in animal feed of antibiotic...

  14. 21 CFR 558.15 - Antibiotic, nitrofuran, and sulfonamide drugs in the feed of animals.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS NEW ANIMAL DRUGS FOR USE IN ANIMAL FEEDS General Provisions § 558.15 Antibiotic, nitrofuran, and sulfonamide drugs in the feed... subtherapeutic (increased rate of gain, disease prevention. etc.) uses in animal feed of antibiotic...

  15. 21 CFR 558.15 - Antibiotic, nitrofuran, and sulfonamide drugs in the feed of animals.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS NEW ANIMAL DRUGS FOR USE IN ANIMAL FEEDS General Provisions § 558.15 Antibiotic, nitrofuran, and sulfonamide drugs in the feed... subtherapeutic (increased rate of gain, disease prevention. etc.) uses in animal feed of antibiotic...

  16. 21 CFR 558.15 - Antibiotic, nitrofuran, and sulfonamide drugs in the feed of animals.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS NEW ANIMAL DRUGS FOR USE IN ANIMAL FEEDS General Provisions § 558.15 Antibiotic, nitrofuran, and sulfonamide drugs in the feed... subtherapeutic (increased rate of gain, disease prevention. etc.) uses in animal feed of antibiotic...

  17. Synthesis of sulfonamides via copper-catalyzed oxidative C-N bond cleavage of tertiary amines.

    PubMed

    Ji, Jing; Liu, Zhengyi; Liu, Ping; Sun, Peipei

    2016-08-01

    A copper-catalyzed coupling reaction of sulfonyl chlorides with tertiary amines via the oxidative C-N bond cleavage of tertiary amines was developed. Sulfonamides were synthesized using this strategy in moderate to good yields. The reaction was applicable to various tertiary amines, as well as sulfonyl chlorides. PMID:27356858

  18. Ferrate promoted oxidative cleavage of sulfonamides: Kinetics and product formation under acidic conditions

    EPA Science Inventory

    Sulfonamide-based antibiotics are often detected in surface waters and secondary wastewater effluents and pose an eminent threat for the development of antibiotic resistance bacteria and genes in aquatic environment. This paper presents the kinetics and stoichiometry of the oxid...

  19. Synthesis and Antimicrobial Activity of the Hybrid Molecules between Sulfonamides and Active Antimicrobial Pleuromutilin Derivative.

    PubMed

    Chen, Liangzhu; Yang, Dexue; Pan, Zhikun; Lai, Lihong; Liu, Jianhua; Fang, Binghu; Shi, Shuning

    2015-08-01

    A series of novel hybrid molecules between sulfonamides and active antimicrobial 14-o-(3-carboxy-phenylsulfide)-mutilin were synthesized, and their in vitro antibacterial activities were evaluated by the broth microdilution. Results indicated that these compounds displayed potent antimicrobial activities in vitro against various drug-susceptible and drug-resistant Gram-positive bacteria such as Staphylococci and streptococci, including methicillin-resistant Staphylococcus aureus, and mycoplasma. In particular, sulfapyridine analog (6c) exhibited more potent inhibitory activity against Gram-positive bacteria and mycoplasma, including Staphylococcus aureus (MIC = 0.016-0.063 μg/mL), methicillin-resistant Staphylococcus aureus (MIC = 0.016 μg/mL), Streptococcus pneumoniae (MIC = 0.032-0.063 μg/mL), Mycoplasma gallisepticum (MIC = 0.004 μg/mL), with respect to other synthesized compounds and reference drugs sulfonamide (MIC = 8-128 μg/mL) and valnemulin (MIC = 0.004-0.5 μg/mL). Furthermore, comparison between MIC values of pleuromutilin-sulfonamide hybrids 6a-f with pleuromutilin parent compound 3 revealed that these modifications at 14 position side chain of the pleuromutilin with benzene sulfonamide could greatly improve the antibacterial activity especially against Gram-positives. PMID:25431015

  20. ELISA for sulfonamides and its application for screening in water contamination

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Two sulfonamide enzyme linked immunosorbent assays (ELISAs) were tested for their suitability in analyte measurement in wastewater from various stages in wastewater treatment plants (WWTPs), the river into which the wastewater is discharged, and two swine rearing facilities. The sulfamethoxazole EL...

  1. Diverse N-Heterocyclic Ring Systems via Aza-Heck Cyclizations of N-(Pentafluorobenzoyloxy)sulfonamides.

    PubMed

    Hazelden, Ian R; Ma, Xiaofeng; Langer, Thomas; Bower, John F

    2016-09-01

    Aza-Heck cyclizations initiated by oxidative addition of Pd(0) -catalysts into the N-O bond of N-(pentafluoro-benzoyloxy)sulfonamides are described. These studies, which encompass only the second class of aza-Heck reaction developed to date, provide direct access to diverse N-heterocyclic ring systems. PMID:27460965

  2. Rapid immunochemical analysis of the sulfonamide-sugar conjugated fraction of antibiotic contaminated honey samples.

    PubMed

    Muriano, A; Chabottaux, V; Diserens, J-M; Granier, B; Sanchez-Baeza, F; Marco, M-P

    2015-07-01

    A rapid high-throughput immunochemical screening (HtiS) procedure for the analysis of the sulfonamide (SA)-sugar conjugated fraction of antibiotic contaminated honey samples has been developed. Studies performed with this matrix have indicated that sulfonamide antibiotics are conjugated to sugars rapidly and quantitatively, providing samples with very low SA immunoreactivity. Therefore, sulfonamides must be first released before the analysis, and for this purpose, a simple and fast sample preparation procedure has been established consisting of hydrolyzing the sample for 5 min, adjusting the pH and buffering the sample prior to the immunochemical analysis. Under these conditions, honey samples could be directly analyzed without any additional sample treatment, other than dilution. Recovery values of the whole analytical procedure were greater than 85%. The analysis of the same samples without the hydrolysis provided recovery values below 5%. Selectivity studies performed in hydrolyzed honey samples revealed that nine relevant sulfonamide antibiotics can be detected with limit of detection (LOD) values below the action limits established by some EU countries (Belgium, 20 μg kg(-1), United Kingdom or Switzerland, 50 μg kg(-1)). PMID:25704696

  3. Multicomponent ternary cocrystals of the sulfonamide group with pyridine-amides and lactams.

    PubMed

    Bolla, Geetha; Nangia, Ashwini

    2015-11-01

    SMBA was selected as a bifunctional sulfa drug to design ternary cocrystals with pyridine amides and lactam coformers. Supramolecular assembly of five ternary cocrystals of p-sulfonamide benzoic acid with nicotinamide and 2-pyridone is demonstrated and reproducible heterosynthons are identified for crystal engineering. PMID:26355724

  4. Development of Sulfonamide Photoaffinity Inhibitors for Probing Cellular γ-Secretase.

    PubMed

    Crump, Christina J; Murrey, Heather E; Ballard, T Eric; Am Ende, Christopher W; Wu, Xianzhong; Gertsik, Natalya; Johnson, Douglas S; Li, Yue-Ming

    2016-08-17

    γ-Secretase is a multiprotein complex that catalyzes intramembrane proteolysis associated with Alzheimer's disease and cancer. Here, we have developed potent sulfonamide clickable photoaffinity probes that target γ-secretase in vitro and in cells by incorporating various photoreactive groups and walking the clickable alkyne handle to different positions around the molecule. We found that benzophenone is preferred over diazirine as a photoreactive group within the sulfonamide scaffold for labeling γ-secretase. Intriguingly, the placement of the alkyne at different positions has little effect on probe potency but has a significant impact on the efficiency of labeling of γ-secretase. Moreover, the optimized clickable photoprobe, 163-BP3, was utilized as a cellular probe to effectively assess the target engagement of inhibitors with γ-secretase in primary neuronal cells. In addition, biotinylated 163-BP3 probes were developed and used to capture the native γ-secretase complex in the 3-[(3-cholamidopropyl)dimethylammonio]-2-hydroxy-1-propanesulfonate (CHAPSO) solubilized state. Taken together, these next generation clickable and biotinylated sulfonamide probes offer new tools to study γ-secretase in biochemical and cellular systems. Finally, the data provide insights into structural features of the sulfonamide inhibitor binding site in relation to the active site and into the design of clickable photoaffinity probes. PMID:27253220

  5. Improved Cav2.2 Channel Inhibitors through a gem-Dimethylsulfone Bioisostere Replacement of a Labile Sulfonamide.

    PubMed

    Shao, Pengcheng P; Ye, Feng; Chakravarty, Prasun K; Herrington, James B; Dai, Ge; Bugianesi, Randal M; Haedo, Rodolfo J; Swensen, Andrew M; Warren, Vivien A; Smith, McHardy M; Garcia, Maria L; McManus, Owen B; Lyons, Kathryn A; Li, Xiaohua; Green, Mitchell; Jochnowitz, Nina; McGowan, Erin; Mistry, Shruti; Sun, Shu-Yu; Abbadie, Catherine; Kaczorowski, Gregory J; Duffy, Joseph L

    2013-11-14

    We report the investigation of sulfonamide-derived Cav2.2 inhibitors to address drug-metabolism liabilities with this lead class of analgesics. Modification of the benzamide substituent provided improvements in both potency and selectivity. However, we discovered that formation of the persistent 3-(trifluoromethyl)benzenesulfonamide metabolite was an endemic problem in the sulfonamide series and that the replacement of the center aminopiperidine scaffold failed to prevent this metabolic pathway. This issue was eventually addressed by application of a bioisostere strategy. The new gem-dimethyl sulfone series retained Cav2.2 potency without the liability of the circulating sulfonamide metabolite. PMID:24900606

  6. Improved Cav2.2 Channel Inhibitors through a gem-Dimethylsulfone Bioisostere Replacement of a Labile Sulfonamide

    PubMed Central

    2013-01-01

    We report the investigation of sulfonamide-derived Cav2.2 inhibitors to address drug-metabolism liabilities with this lead class of analgesics. Modification of the benzamide substituent provided improvements in both potency and selectivity. However, we discovered that formation of the persistent 3-(trifluoromethyl)benzenesulfonamide metabolite was an endemic problem in the sulfonamide series and that the replacement of the center aminopiperidine scaffold failed to prevent this metabolic pathway. This issue was eventually addressed by application of a bioisostere strategy. The new gem-dimethyl sulfone series retained Cav2.2 potency without the liability of the circulating sulfonamide metabolite. PMID:24900606

  7. Multi-residue analysis of pesticides in traditional Chinese medicines using gas chromatography-negative chemical ionisation tandem mass spectrometry.

    PubMed

    Nie, Jing; Miao, Shui; Lehotay, Steven J; Li, Wen-Ting; Zhou, Heng; Mao, Xiu-Hong; Lu, Ji-Wei; Lan, Lan; Ji, Shen

    2015-01-01

    In this study, a residue analysis method for the simultaneous determination of 107 pesticides in traditional Chinese medicines (TCMs), Angelica sinensis, A. dahurica, Leonurus heterophyllus Sweet, Pogostemon cablin and Lonicera japonica Thunb., was developed using gas chromatography coupled with tandem mass spectrometry in negative chemical ionisation mode (GC-NCI-MS/MS). NCI has advantages of high sensitivity and selectivity to chemicals with electron-withdrawing groups, and yields low background interference. For sample preparation, QuEChERS (quick, easy, cheap, effective, rugged and safe) was applied. Due to the unique characteristics of TCMs, the clean-up step was optimised by adjusting amounts of primary secondary amine, C18, graphitised carbon black and silica sorbents. Validation was mainly performed by determining analyte recoveries at four different spiking concentrations of 10, 50, 100 and 200 ng g(-1), with seven replicates at each concentration. Method trueness, precision, linearity of calibration curves, lowest calibrated levels (LCLs) and matrix effects were determined to demonstrate method and instrument performance. Among the 107 pesticides tested, approximately 80% gave recoveries from 80% to 110% and < 10% relative standard deviation (RSD). The LCLs for nearly all pesticides were 5 ng g(-1), and as low as 0.1 ng g(-1) for dichlofenthion, endosulfan sulphate, flumetralin, isofenphos-methyl, methyl-pentachlorophenyl sulphide and trifluralin. The results indicate that GC-NCI-MS/MS is an excellent technique for quantitative and qualitative analysis of targeted GC-amenable pesticides at ultra-trace levels, especially in complex matrices such as TCMs. PMID:26125677

  8. Determination of sulfonamide antibiotics and metabolites in liver, muscle and kidney samples by pressurized liquid extraction or ultrasound-assisted extraction followed by liquid chromatography-quadrupole linear ion trap-tandem mass spectrometry (HPLC-QqLIT-MS/MS).

    PubMed

    Hoff, Rodrigo Barcellos; Pizzolato, Tânia Mara; Peralba, Maria do Carmo Ruaro; Díaz-Cruz, M Silvia; Barceló, Damià

    2015-03-01

    Sulfonamides are widely used in human and veterinary medicine. The presence of sulfonamides residues in food is an issue of great concern. Throughout the present work, a method for the targeted analysis of 16 sulfonamides and metabolites residue in liver of several species has been developed and validated. Extraction and clean-up has been statistically optimized using central composite design experiments. Two extraction methods have been developed, validated and compared: i) pressurized liquid extraction, in which samples were defatted with hexane and subsequently extracted with acetonitrile and ii) ultrasound-assisted extraction with acetonitrile and further liquid-liquid extraction with hexane. Extracts have been analyzed by liquid chromatography-quadrupole linear ion trap-tandem mass spectrometry. Validation procedure has been based on the Commission Decision 2002/657/EC and included the assessment of parameters such as decision limit (CCα), detection capability (CCβ), sensitivity, selectivity, accuracy and precision. Method׳s performance has been satisfactory, with CCα values within the range of 111.2-161.4 µg kg(-1), limits of detection of 10 µg kg(-1) and accuracy values around 100% for all compounds. PMID:25618734

  9. Fabrication of CoFe2O4-graphene nanocomposite and its application in the magnetic solid phase extraction of sulfonamides from milk samples.

    PubMed

    Li, Yazhen; Wu, Xuewen; Li, Zhaoqian; Zhong, Shuxian; Wang, Weiping; Wang, Aijun; Chen, Jianrong

    2015-11-01

    In the present study, a graphene-based magnetic nanocomposite (CoFe2O4-graphene, CoFe2O4-G) was synthesized and used successfully as an adsorbent for the magnetic solid phase extraction (MSPE) of sulfonamides for the first time. The surface morphologies and structures of the CoFe2O4-G nanocomposite were investigated by scanning electron microscopy (SEM), FT-IR, UV-vis spectroscopy, X-ray diffraction (XRD) and vibration sample magnetometer (VSM). Five sulfonamides, including sulfamerazine, sulfamethizole, sulfadoxine, sulfamethoxazole and sulfisoxazole were used as model analytes to evaluate the enrichment properties of the prepared adsorbent in MSPE. After preconcentration, the adsorbent could be conveniently separated from the aqueous samples by an external magnet, and the analytes desorbed from adsorbent were determined by high performance liquid chromatography-ultraviolet detection (HPLC-UV). Extraction parameters including sample pH, amount of sorbent, extraction time and desorption conditions were optimized in detail. Under the optimal conditions, good linear relationships between the peak areas and the concentrations of the analytes were obtained. The linear ranges were 0.02-50.00 mg L(-1) with correlation coefficients (r)≧0.9982. The limits of detection were less than 1.59 μg L(-1). Good reproducibility was obtained. The relative standard deviations of intra- and inter-day analysis were less than 4.3% and 6.5%, respectively. The proposed method was successfully applied for the analysis of sulfonamides in milk samples. The average recoveries determined for two milk samples spiked at levels from 5 to 20 μg L(-1) were 62.0-104.3% with relative standard deviations less than 14.0%. In addition, the CoFe2O4-G could be reused after cleaning with acetone and ultrapure water successively. PMID:26452959

  10. The multi-residue determination of coumarin-based anticoagulant rodenticides in animal materials by high-performance liquid chromatography.

    PubMed

    Mundy, D E; Machin, A F

    1982-01-15

    The rodenticides brodifacoum, difenacoum, coumatetralyl and warfarin are determined in animal relicta by high-performance exclusion chromatography on porous silica. The first three compounds are not separated, but are subsequently differentiated by adsorption or reversed-phase high-performance liquid chromatography of the appropriate eluate fraction collected from the exclusion column. The method is rapid, and clean-up (on Sep-Pak silica cartridges) is simple. Mean recoveries from spiked substrates were generally above 80% at levels of 0.1-1.0 mg/kg. Routine limits of determination are about 0.05-0.1 mg/kg for warfarin and about 0.02 mg/kg for the other compounds. If analysis for warfarin is not required, the latter limit can be lowered to about 1 microgram/kg by a slight modification to the clean-up step. PMID:7056833