Sample records for ion exclusion chromatography

  1. Ion-Exclusion Chromatography for Analyzing Organics in Water

    NASA Technical Reports Server (NTRS)

    Sauer, Richard; Rutz, Jeffrey A.; Schultz, John R.

    2006-01-01

    A liquid-chromatography technique has been developed for use in the quantitative analysis of urea (and of other nonvolatile organic compounds typically found with urea) dissolved in water. The technique involves the use of a column that contains an ion-exclusion resin; heretofore, this column has been sold for use in analyzing monosaccharides and food softeners, but not for analyzing water supplies. The prior technique commonly used to analyze water for urea content has been one of high-performance liquid chromatography (HPLC), with reliance on hydrophobic interactions between analytes in a water sample and long-chain alkyl groups bonded to an HPLC column. The prior technique has proven inadequate because of a strong tendency toward co-elution of urea with other compounds. Co-elution often causes the urea and other compounds to be crowded into a narrow region of the chromatogram (see left part of figure), thereby giving rise to low chromatographic resolution and misidentification of compounds. It is possible to quantitate urea or another analyte via ultraviolet- and visible-light absorbance measurements, but in order to perform such measurements, it is necessary to dilute the sample, causing a significant loss of sensitivity. The ion-exclusion resin used in the improved technique is sulfonated polystyrene in the calcium form. Whereas the alkyl-chain column used in the prior technique separates compounds on the basis of polarity only, the ion-exclusion-resin column used in the improved technique separates compounds on the basis of both molecular size and electric charge. As a result, the degree of separation is increased: instead of being crowded together into a single chromatographic peak only about 1 to 2 minutes wide as in the prior technique, the chromatographic peaks of different compounds are now separated from each other and spread out over a range about 33 minutes wide (see right part of figure), and the urea peak can readily be distinguished from the other peaks. Although the analysis takes more time in the improved technique, this disadvantage is offset by two important advantages: Sensitivity is increased. The minimum concentration of urea that can be measured is reduced (to between 1/5 and 1/3 of that of the prior technique) because it is not necessary to dilute the sample. The separation of peaks facilitates the identification and quantitation of the various compounds. The resolution of the compounds other than urea makes it possible to identify those compounds by use of mass spectrometry.

  2. Instrumentation: Ion Chromatography.

    ERIC Educational Resources Information Center

    Fritz, James S.

    1987-01-01

    Discusses the importance of ion chromatography in separating and measuring anions. The principles of ion exchange are presented, along with some applications of ion chromatography in industry. Ion chromatography systems are described, as well as ion pair and ion exclusion chromatography, column packings, detectors, and programming. (TW)

  3. Size-exclusion chromatography of lignin as ion-pair complex

    Microsoft Academic Search

    A Majcherczyk; A Hüttermann

    1997-01-01

    A high-performance ion-pair size-exclusion chromatography method was developed for analysis of underivatised lignin samples using styrene–divinylbenzene gel columns with tetrahydrofuran as solvent. An extraction method using the quaternary amine methyltrioctylammonium chloride allowed quantitative extraction of kraft lignin, lignosulfonic acids and Organosolv lignins from alkaline solution to various organic solvents. Quaternary-amine complexes of lignins formed were analysed by an ion-pair type

  4. A process for separating acid-sugar mixtures using ion exclusion chromatography

    SciTech Connect

    Hester, R.D.; Hartfield, S.W. [University of Southern Mississippi, Hattiesburg, MS (United States); Farina, G.E. [Tennessee Valley Authority, Muscle Shoals, AL (United States)

    1994-10-01

    Work using a low-temperature concentrated sulfuric acid hydrolysis process to convert the cellulosic fraction of corn stover to monomeric sugars demonstrated the high conversion efficiencies possible with that process. The TVA work also confirmed the need for a cost-effective acid-sugar separation process. A preparative-scale ion-exclusion chromatography (IEC) system was designed, constructed, and tested with a variety of synthetic solutions and actual hydrolyzates. Although significant dispersion was observed initially, design changes were effective in minimizing this phenomenon. Data collected during the operation of the preparative-scale system were used in the design and construction of an IEC miniplant capable of processing larger volumes of synthetic solutions or hydrolyzates and in the design of an extraction-assisted IEC system. The data were also used to assess the viability of a continuous feed IEC system. This paper includes a discussion of the IEC process, provides overall material balances for various IEC process scenarios, and presents a discussion on process economics.

  5. Separation of acid and sugar by ion exclusion chromatography. An application in the conversion of cellulose to ethanol

    SciTech Connect

    Hartfield, S.; Hester, R. [Univ. of Southern Mississippi, Hattiesburg, MS (United States)

    1993-12-31

    The production of fuel grade alcohol by fermentation from sugars obtained by the acid hydrolysis of cellulose has been hindered by costly methods of cleansing the acid in the sugar stream. An economical and environmentally acceptable acid-sugar separation process based on ion exclusion chromatography has been developed and analyzed. This process recovers the acid for reuse in hydrolysis without producing landfill waste allowing a concentrated acid hydrolysis process to be commercially feasible.

  6. Vacancy ion-exclusion/adsorption chromatography of aliphatic amines on a polymethacrylate-based weakly basic anion-exchange column.

    PubMed

    Mori, Masanobu; Helaleh, Murad I H; Xu, Qun; Hu, Wenzhi; Ikedo, Mikaru; Ding, Ming-Yu; Taoda, Hiroshi; Tanaka, Kazuhiko

    2004-06-11

    Vacancy ion-exclusion/adsorption chromatography has been applied to investigate the separation behavior of five aliphatic amines (ethylamine, propylamine, butylamine, pentylamine and hexylamine) on a polymethacrylate-based weakly basic anion-exchange column (Tosoh TSKgel DEAE-5PW). This system is consisted of analytes as a mobile phase and water as an injected sample. In the vacancy ion-exclusion/adsorption chromatography, the elution order was as follows: ethylamine < propylamine < butylamine < pentylamine < hexylamine, depending on their hydrophobicity. The retention times of the amines were decreased with decreasing their concentrations in the mobile phase. The retention times and resolutions of the amines were increased by adding a basic compound (e.g., lithium hydroxide or heptylamine) and by increasing the pH of mobile phase (pH > 11). This was because the dissociations of amine samples in the mobile phase were suppressed and thus the hydrophobic adsorption effects were enhanced. The linearity of calibration graphs could be obtained from the peak areas of the amine samples injected to the 0.05, 0.5 and 5 mM of amine mobile phase at pH 11 by heptylamine. The detection limits of aliphatic amines as injected samples were around 1 microM for five aliphatic amines at three different amine mobile phases. From these results, the retention behaviors of aliphatic amines on vacancy ion-exclusion/adsorption chromatography were concluded to be governed by the hydrophobic adsorption effect. PMID:15250414

  7. Determination of some aliphatic carboxylic acids in anaerobic digestion process waters by ion-exclusion chromatography with conductimetric detection on a weakly acidic cation-exchange resin column

    Microsoft Academic Search

    Kazuaki Ito; Yohichi Takayama; Mikaru Ikedo; Masanobu Mori; Hiroshi Taoda; Qun Xu; Wenzhi Hu; Hiroshi Sunahara; Tsuneo Hayashi; Shinji Sato; Takeshi Hirokawa; Kazuhiko Tanaka

    2004-01-01

    The determination of seven aliphatic carboxylic acids, formic, acetic, propionic, isobutyric, n-butyric, isovaleric and n-valeric acids in anaerobic digestion process waters was examined using ion-exclusion chromatography with conductimetric detection. The analysis of these biologically important carboxylic acids is necessary as a measure for evaluating and controlling the process. The ion-exclusion chromatography system employed consisted of polymethacrylate-based weakly acidic cation-exchange resin

  8. Determination of short chain carboxylic acids in vegetable oils and fats using ion exclusion chromatography electrospray ionization mass spectrometry.

    PubMed

    Viidanoja, Jyrki

    2015-02-27

    A new method for quantification of short chain C1-C6 carboxylic acids in vegetable oils and fats by employing Liquid Chromatography Mass Spectrometry (LC-MS) has been developed. The method requires minor sample preparation and applies non-conventional Electrospray Ionization (ESI) liquid phase chemistry. Samples are first dissolved in chloroform and then extracted using water that has been spiked with stable isotope labeled internal standards that are used for signal normalization and absolute quantification of selected acids. The analytes are separated using Ion Exclusion Chromatography (IEC) and detected with Electrospray Ionization Mass Spectrometry (ESI-MS) as deprotonated molecules. Prior to ionization the eluent that contains hydrochloric acid is modified post-column to ensure good ionization efficiency of the analytes. The averaged within run precision and between run precision were generally lower than 8%. The accuracy was between 85 and 115% for most of the analytes. The Lower Limit of Quantification (LLOQ) ranged from 0.006 to 7mg/kg. It is shown that this method offers good selectivity in cases where UV detection fails to produce reliable results. PMID:25627971

  9. Simultaneous determination of NH4+, NO2(-) and NO3(-) by ion-exclusion/anion-exchange chromatography on a strongly basic anion-exchange resin with basic eluent.

    PubMed

    Mori, Masanobu; Hironaga, Takahiro; Itabashi, Hideyuki; Nakatani, Nobutake; Kozaki, Daisuke; Tanaka, Kazuhiko

    2012-04-01

    Ion-exclusion/anion-exchange chromatography (IEC/AEC) on a combination of a strongly basic anion-exchange resin in the OH(-)-form with basic eluent has been developed. The separation mechanism is based on the ion-exclusion/penetration effect for cations and the anion-exchange effect for anions to anion-exchange resin phase. This system is useful for simultaneous separation and determination of ammonium ion (NH4+), nitrite ion (NO2(-)), and nitrate ion (NO3(-)) in water samples. The resolution of analyte ions can be manipulated by changing the concentration of base in eluent on a polystyrene-divinylbenzene based strongly basic anion-exchange resin column. In this study, several separation columns, which consisted of different particle sizes, different functional groups and different anion-exchange capacities, were compared. As the results, the separation column with the smaller anion-exchange capacity (TSKgel Super IC-Anion) showed well-resolved separation of cations and anions. In the optimization of the basic eluent, lithium hydroxide (LiOH) was used as the eluent and the optimal concentration was concluded to be 2 mmol/L, considering the resolution of analyte ions and the whole retention times. In the optimal conditions, the relative standard deviations of the peak areas and the retention times of NH4+, NO2(-), and NO3(-) ranged 1.28% - 3.57% and 0.54% - 1.55%, respectively. The limits of detection at signal-to-noise of 3 were 4.10 micromol/L for NH4+, 1.87 micromol/L for NO2(-) and 2.83 micromol/L for NO3(-). PMID:22799190

  10. Determination of furanic compounds in traditional balsamic vinegars by ion-exclusion liquid chromatography and diode-array detection.

    PubMed

    Chinnici, Fabio; Masino, Francesca; Antonelli, Andrea

    2003-07-01

    A method for the determination of furanic compounds in traditional balsamic vinegars is proposed. It is based on ion-exclusion chromatographic separation and diode-array detection of furans through an isocratic elution with 0.01 N phosphoric acid and 16% acetonitrile. Preliminary trials on standard compounds stability in heat-acidic conditions are also performed. In all the 19 samples analyzed, 2-furoic acid, 5 HMF, and furfural are found. No sample contains 4-hydroxy-2,5-dimethyl-3-(2H)-furanone (DHMF); 2-acetylfuran; or furfuryl alcohol. Three unknown compounds are also detected. The last eluting of these compounds is identified as 5-acethoxymethylfurfural, and, notwithstanding a partial hydrolysis in our chromatographic conditions, its quantitation can be carried out. PMID:12935302

  11. Ion Pairing Chromatography

    Microsoft Academic Search

    Teresa Cecchi

    2008-01-01

    The present state of ion-pair chromatography (IPC) is reviewed. Emphasis is placed on the theoretical modeling of the retention behavior of charged, zwitterionic, and neutral solutes, since the theory provides the generally good understanding of the factors affecting the separation. Although stoichiometric models were credited with the first easy-to-understand demonstration of the retention mechanism of IPC, they were thermodynamic models,

  12. A novel ion-exclusion chromatography-mass spectrometry method to measure concentrations and cycling rates of carbohydrates and amino sugars in freshwaters.

    PubMed

    Hor?ák, Karel; Pernthaler, Jakob

    2014-10-24

    The concentrations of free neutral carbohydrates and amino sugars were determined in freshwater samples of distinct matrix complexity, including meso-, eu- and dystrophic lakes and ponds, using high-performance ion-exclusion chromatography (HPIEC) coupled to mass spectrometry (MS). In contrast to other methods, our approach allowed the quantification of free neutral carbohydrates and amino sugars at low nM concentrations without derivatization, de-salting or pre-concentration. New sample preparation procedures were applied prior to injection employing syringe and hollow fiber filtration. Analytes were separated on a strong cation exchange resin under 100% aqueous conditions using 0.1% formic acid as a mobile phase. To minimize background noise in MS, analytes were detected in a multiple reaction monitoring scan mode with double ion filtering. Detection limits of carbohydrates and amino sugars ranged between 0.2 and 2nM at a signal-to-noise ratio >5. Error ranged between 1 and 12% at 0.5-500nM levels. Using a stable isotope dilution approach, both the utilization and recycling of glucose in Lake Zurich was observed. In contrast, N-acetyl-glucosamine was equally rapidly consumed but there was no visible de novo production. The simple and rapid sample preparation makes our protocol suitable for routine analyses of organic compounds in freshwater samples. Application of stable isotope tracers along with accurate measures of carbohydrate and amino sugar concentrations enables novel insights into the compound in situ dynamics. PMID:25242224

  13. Size exclusion chromatography does not require pores

    PubMed Central

    Brooks, Donald E.; Haynes, Charles A.; Hritcu, Doina; Steels, Bradley M.; Müller, Werner

    2000-01-01

    Separation of macromolecules on the basis of their molecular weight by size exclusion chromatography has long been considered to be caused by the geometry-dependent partition of macromolecules between a continuous phase and the porous interior of a gel or cross-linked bead. The volume of a pore accessible to a solute is limited by its relative dimensions, so larger molecules will have access to a smaller volume and will remain in a bead for a shorter time than smaller solutes. Our recent alternate picture proposes that the partition coefficient can be calculated from a thermodynamic model for the free energy of mixing of the solute with the gel phase. Size-dependent exclusion caused by the unfavorable entropy of mixing associated with the partition is predicted; the magnitude of the effect is modified by enthalpic interactions between the solute and the gel phase. This concept is extended here to describe the partition of macromolecules into a layer of terminally attached polymer chains grafted onto a solid bead. Both simple mean field and self-consistent field theory calculations predict size-dependent entropic exclusion. Experimental results obtained with neutral polymer chains grafted onto solid polystyrene latex beads confirm the predictions. PMID:10852951

  14. Using ion chromatography to monitor haloacetic acids in drinking water: a review of current technologies

    Microsoft Academic Search

    Brett Paull; Leon Barron

    2004-01-01

    A review of the application of ion chromatography to the determination of haloacetic acids in drinking water is given. As it requires no sample derivatisation, ion chromatography in its various modes, such as ion-exchange, ion-interaction and ion-exclusion chromatography, is increasingly being investigated as a simpler alternative to gas chromatographic methods for the determination of polar disinfection by-products (DBPs) in drinking

  15. Direct determination of Si isotope ratios in natural waters and commercial Si standards by ion exclusion chromatography multicollector inductively coupled plasma mass spectrometry.

    PubMed

    Yang, Lu; Zhou, Lian; Hu, Zhaochu; Gao, Shan

    2014-09-16

    Silicon isotope ratios in natural waters and several commercial Si standards were determined by online ion exclusion chromatography (IEC) multicollector inductively couple plasma mass spectrometry (MC-ICPMS). As recent studies have shown that mass-independent fractionation (MIF) also exists in MC-ICPMS, e.g., Nd, Ce, W, Sr, Hf, Ge, Hg, and Pb isotopes, the nature of mass bias for Si isotopes was thus investigated. MIF was observed for Si isotopes on both Neptune and Neptune plus MC-ICPMS instruments in this study. Therefore, a standard-sample bracketing (SSB) mass bias correction model, capable of correcting both mass-dependent and mass-independent bias, was employed to obtain accurate Si isotope ratio results in all samples by using NBS28 Si standard as the bracketing standard. Medium resolution was used for all measurements in order to resolve polyatomic interferences on Si isotopes. NBS28 Si standard solutions prepared in nutrient-free seawater and 0.1% NaOH matrix, respectively, were used for the method validation and subjected to the online IEC MC-ICPMS determination of Si isotope ratios. Values of -0.01 ± 0.06 and 0.00 ± 0.06 ‰ (1 SD, n = 10) and -0.01 ± 0.03 and 0.01 ± 0.06 ‰ (1 SD, n = 10) for ?(29/28)Si and ?(30/28)Si, respectively, were obtained, confirming accurate results can be obtained using the reported method for natural waters. Significant variations in Si isotope ratios from -0.72 ± 0.09 to -0.24 ± 0.03 ‰ (1 SD, n = 10) and -1.36 ± 0.11 to -0.46 ± 0.04 ‰ (1 SD, n = 10) for ?(29/28)Si and ?(30/28)Si, respectively, were found among commercial Si standards of NIST SRM3150, SCP Si, and Sigma-Aldrich Si. Values of -0.06 ± 0.07 and -0.20 ± 0.11 ‰ (1 SD, n = 10) for ?(29/28)Si and ?(30/28)Si, respectively, were obtained for the MOOS-3 seawater whereas 0.59 ± 0.11 and 1.19 ± 0.15 ‰ (1SD, n = 10) for ?(29/28)Si and ?(30/28)Si, respectively, were obtained for the SLRS-5 river water. To the best of our knowledge this is the first report of an application of online IEC MC-ICPMS for the high accuracy and precision determination of Si isotope ratios in natural waters. The reported method provides for a relatively rapid (10 min per run) and simple online technique that requires no sample pretreatment for the Si isotope ratio measurements. PMID:25162683

  16. Detection and data analysis in size exclusion chromatography

    SciTech Connect

    Provder, T. (ed.)

    1987-01-01

    Specific topics covered in this symposium on site exclusion chromatography are of interest under the broad topic of energy research. namely, the chemical analysis of siloxanes as the chemical analysis of coal liquids.

  17. Investigation and interpretation of band broadening in size exclusion chromatography.

    PubMed

    Busnel, J P; Foucault, F; Denis, L; Lee, W; Chang, T

    2001-09-28

    Study of Band Broadening occurring in Size Exclusion Chromatography (SEC) is reported using very narrow PS standards obtained and characterised by Temperature Gradient Interaction Chromatography (TGIC). Chromatograms are fitted by Exponentially Modified Gaussian functions (EMG) and mapping of band broadening is obtained for different column sets. Interpretation of the skewing of the chromatograms is proposed with a new model using Brownian motion properties inside the pores. That explains why band broadening and tailing become so important near total exclusion volume. PMID:11681580

  18. Investigation and interpretation of band broadening in size exclusion chromatography

    Microsoft Academic Search

    J. P. Busnel; F. Foucault; L. Denis; W. Lee; T. Chang

    2001-01-01

    Study of Band Broadening occurring in Size Exclusion Chromatography (SEC) is reported using very narrow PS standards obtained and characterised by Temperature Gradient Interaction Chromatography (TGIC). Chromatograms are fitted by Exponentially Modified Gaussian functions (EMG) and mapping of band broadening is obtained for different column sets. Interpretation of the skewing of the chromatograms is proposed with a new model using

  19. Monolithic Phases for Ion Chromatography

    NASA Astrophysics Data System (ADS)

    Nordborg, Anna; Hilder, Emily F.; Haddad, Paul R.

    2011-07-01

    Monolithic media are continuing to increase in popularity in chromatographic applications, and the ongoing use of commercially available materials in ion chromatography (IC) has made monoliths a viable alternative to packed-bed columns for routine use. We discuss different strategies for the synthesis of polymeric and silica monoliths with ion-exchange functionality, such as direct incorporation of ion-exchange functionality during monolith preparation and different postpolymerization alterations such as grafting and coating. The formulations and strategies presented are focused on materials intended for use in IC. We also discuss strategies for materials characterization, with emphasis on nondestructive techniques for the characterization of monolith surface functionality, especially those with applicability to in situ analysis. Finally, we describe selected IC applications of polymeric and silica monoliths published from 2008 to 2010.

  20. Monitoring xanthan quality during fermentation by size exclusion chromatography

    Microsoft Academic Search

    H. Herbst; H.-U. Peters; I.-S. Suh; A. Schumpe; W.-D. Deckwer

    1988-01-01

    Summary Xanthan concentration and molecular weight distribution are determined by size exclusion chromatography in the fermentation medium after dilution and cell removal by centrifugation. The analysis is rapid enough for process control. During a batch fermentation, the average molecular weight is found to be in the range of 7.2–9.3·106 g\\/mole and to run through a maximum.

  1. A novel multidimensional protein identification technology approach combining protein size exclusion prefractionation, peptide zwitterion-ion hydrophilic interaction chromatography, and nano-ultraperformance RP chromatography/nESI-MS2 for the in-depth analysis of the serum proteome and phosphoproteome: application to clinical sera derived from humans with benign prostate hyperplasia.

    PubMed

    Garbis, Spiros D; Roumeliotis, Theodoros I; Tyritzis, Stavros I; Zorpas, Kostas M; Pavlakis, Kitty; Constantinides, Constantinos A

    2011-02-01

    The current proof-of-principle study was aimed toward development of a novel multidimensional protein identification technology (MudPIT) approach for the in-depth proteome analysis of human serum derived from patients with benign prostate hyperplasia (BPH) using rational chromatographic design principles. This study constituted an extension of our published work relating to the identification and relative quantification of potential clinical biomarkers in BPH and prostate cancer (PCa) tissue specimens. The proposed MudPIT approach encompassed the use of three distinct yet complementary liquid chromatographic chemistries. High-pressure size-exclusion chromatography (SEC) was used for the prefractionation of serum proteins followed by their dialysis exchange and solution phase trypsin proteolysis. The tryptic peptides were then subjected to offline zwitterion-ion hydrophilic interaction chromatography (ZIC-HILIC) fractionation followed by their online analysis with reversed-phase nano-ultraperformance chromatography (RP-nUPLC) hyphenated to nanoelectrospray ionization-tandem mass spectrometry using an ion trap mass analyzer. For the spectral processing, the sequential use of the SpectrumMill, Scaffold, and InsPecT software tools was applied for the tryptic peptide product ion MS(2) spectral processing, false discovery rate (FDR) assessment, validation, and protein identification. This milestone serum analysis study allowed the confident identification of over 1955 proteins (p ? 0.05; FDR ? 5%) with a broad spectrum of biological and physicochemical properties including secreted, tissue-specific proteins spanning approximately 12 orders of magnitude as they occur in their native abundance levels in the serum matrix. Also encompassed in this proteome was the confident identification of 375 phosphoproteins (p ? 0.05; FDR ? 5%) with potential importance to cancer biology. To demonstrate the performance characteristics of this novel MudPIT approach, a comparison was made with the proteomes resulting from the immunodepletion of the high abundant albumin and IgG proteins with offline first dimensional tryptic peptide separation with both ZIC-HILIC and strong cation exchange (SCX) chromatography and their subsequent online RP-nUPLC-nESI-MS(2) analysis. PMID:21174401

  2. Optimization Strategies in Ion Chromatography

    Microsoft Academic Search

    Tomislav Bolan?a

    2007-01-01

    The ion chromatographer is often concerned with the separation of complex mixtures with a variable behavior of their components, which makes good resolution and reasonable analysis time sometimes extremely difficult. Several optimization strategies have been proposed to solve this problem. The most reliable and less time consuming strategies apply resolution criteria based on theoretical or empirical retention models to describe

  3. Analyzing insulin samples by size-exclusion chromatography: a column degradation study.

    PubMed

    Teska, Brandon M; Kumar, Amit; Carpenter, John F; Wempe, Michael F

    2015-04-01

    Investigating insulin analogs and probing their intrinsic stability at physiological temperature, we observed significant degradation in the size-exclusion chromatography (SEC) signal over a moderate number of insulin sample injections, which generated concerns about the quality of the separations. Therefore, our research goal was to identify the cause(s) for the observed signal degradation and attempt to mitigate the degradation in order to extend SEC column lifespan. In these studies, we used multiangle light scattering, nuclear magnetic resonance, and gas chromatography-mass spectrometry methods to evaluate column degradation. The results from these studies illustrate: (1) that zinc ions introduced by the insulin product produced the observed column performance issues; and (2) that including ethylenediaminetetraacetic acid, a zinc chelator, in the mobile phase helped to maintain column performance. PMID:25581527

  4. Ion-Exchange Chromatography in Alcohol

    Microsoft Academic Search

    K. K. Carroll

    1955-01-01

    IN the technique of ion-exchange chromatography, the order in which compounds are eluted from a column depends basically upon differences in their ionization constants; but other factors modify and in many instances reverse the expected order1. This is illustrated in Fig. 1, where the elution peaks of a number of acids from a `Dowex' resin are plotted against their pK

  5. Semimicro ion chromatography of iodide in seawater

    Microsoft Academic Search

    Kazuaki Ito

    1999-01-01

    Large sample volume injections including both on-column analyte focusing and on-column matrix elimination techniques were examined for semi-micro ion chromatography of trace iodide (I?) in seawater. A semi-microcolumn (35×1 mm I.D.) packed with styrene–divinylbenzene copolymer with high anion-exchange capacity and a mobile phase of 0.03 M NaClO4+0.5 M NaCl+5 mM sodium phosphate buffer, pH 6.0, was used. Iodide in seawater

  6. Improving size-exclusion chromatography separation for glycogen.

    PubMed

    Sullivan, Mitchell A; Powell, Prudence O; Witt, Torsten; Vilaplana, Francisco; Roura, Eugeni; Gilbert, Robert G

    2014-03-01

    Glycogen is a hyperbranched glucose polymer comprised of glycogen ? particles, which can also form much larger composite ? particles. The recent discovery using size-exclusion chromatography (SEC) that fewer, smaller, ? particles are found in diabetic-mouse liver compared to healthy mice highlights the need to achieve greater accuracy in the size separation methods used to analyze ? and ? particles. While past studies have used dimethyl sulfoxide as the SEC eluent to analyze the molecular size and structure of native glycogen, an aqueous eluent has not been rigorously tested and compared with dimethyl sulfoxide. The conditions for SEC of pig-liver glycogen, phytoglycogen and oyster glycogen were optimized by comparing two different eluents, aqueous 50 mM NH?NO?/0.02% NaN? and dimethyl sulfoxide/0.5% LiBr, run through different column materials and pore sizes at various flow rates. The aqueous system gave distinct size separation of ?- and ?-particle peaks, allowing for a more detailed and quantitative analysis and comparison between liver glycogen samples. This greater resolution has also revealed key differences between the structure of liver glycogen and phytoglycogen. PMID:24508396

  7. P R O D U C T N O T E Size Exclusion Chromatography Sorbents

    E-print Network

    Lebendiker, Mario

    BIOSEPRA ® ULTROGEL ® AcA 1 P R O D U C T N O T E Ultrogel® AcA Size Exclusion Chromatography distribution BioSepra Ultrogel AcA sorbents from Pall® are a range of composite sorbents for size exclusion. They are suitable for medi- um and large scale applications. The principal characteristics of Ultrogel AcA

  8. Liquid Chromatography at Critical Conditions: Balancing size exclusion and adsorption in nanopores

    NASA Astrophysics Data System (ADS)

    Abdulahad, Asem; Amos, Jeffrey; Ryu, Chang

    2009-03-01

    Liquid chromatography at critical condition (LCCC) is a measure to identify thermodynamic conditions, in which polymers elute independently of molar mass during high performance liquid chromatography. Under these critical conditions the entropic exclusions that dominate size exclusion chromatography (SEC) and the enthalpic adsorption that governs adsorption-based interaction chromatography (IC) are said to negate one another resulting in simultaneous elution of the polymer of different molecular weights. Using multiple C18-bonded silica columns with different average nanopore sizes (from 5 nm to 30 nm), we will study the LCCC conditions of PS in methylene chloride/acetonitrile solvent mixture at different temperature. In addition, we will show that the separation of polystyrene can be fine tuned using a refined temperature gradient interaction chromatography (TGIC) that employs multiple columns of varying pore size in sequence.

  9. Antioxidant activity of whey protein fractions isolated by gel exclusion chromatography and protease treatment

    Microsoft Academic Search

    Tu?ba Bayram; Murat Pekmez; Nazl? Arda; A. Süha Yalç?n

    2008-01-01

    Whey proteins were isolated from whey powder by a combination of gel exclusion chromatography and protease (pepsin or trypsin) treatment. Whey solution (6g\\/dl) was applied to Sephadex G-200 column chromatography and three fractions were obtained. Gel electrophoresis (SDS-PAGE) was used to identify the fractions; the first one contained immunoglobulins and bovine serum albumin, the second contained ?-lactoglobulin and ?-lactalbumin whereas

  10. Molecular Characterization of Multivalent Bioconjugates by Size-Exclusion Chromatography with Multiangle Laser Light Scattering

    E-print Network

    Schaffer, David V.

    with Multiangle Laser Light Scattering Jacob F. Pollock,, Randolph S. Ashton,§ Nikhil A. Rode, David V. Schaffer polyvalent bioactive conjugates. In this study, size-exclusion chromatography with multiangle laser light scattering was paired with refractive index detection and ultraviolet spectroscopy (SEC

  11. Purification and Characterization of Microbial Hyaluronic Acid by Solvent Precipitation and Size-Exclusion Chromatography

    Microsoft Academic Search

    Anayla S. Sousa; Artemízia P. Guimarães; Caroline V. Gonçalves; Ivanildo J. Silva Jr; Celio L. Cavalcante Jr; Diana C. S. Azevedo

    2009-01-01

    Samples of hyaluronic acid (HA) produced by submerged fermentation using a synthetic culture medium were recovered, purified, fractioned, and characterized using solvent precipitation and size-exclusion chromatography (SEC). The samples showed a wide molar mass distribution in the range 10–10 Da, most of which had an average molar mass between 10 and 10 Da after purification by sequential precipitations. Fractions of

  12. imagination at work Data file 29-0452-69AA Size exclusion chromatography

    E-print Network

    Lebendiker, Mario

    imagination at work Data file 29-0452-69AA Size exclusion chromatography SuperdexTM 200 Increase 200 Increase columns is based on a high-flow agarose base matrix with good pressure/flow properties.2/300, Superdex 200 Increase 5/150 GL, and Superdex 200 Increase 10/300 GL columns. #12;2 29-0452-69AA

  13. Separation of single-walled carbon nanotubes by 1-dodecanol-mediated size-exclusion chromatography.

    PubMed

    Flavel, Benjamin S; Kappes, Manfred M; Krupke, Ralph; Hennrich, Frank

    2013-04-23

    A simple, single-column, high-throughput fractionation procedure based on size-exclusion chromatography of aqueous sodium dodecyl sulfate suspensions of single-walled carbon nanotubes (SWCNTs) is presented. This procedure is found to yield monochiral or near monochiral SWCNT fractions of semiconducting SWCNTs. Unsorted and resulting monochiral suspensions are characterized using optical absorption and photoluminescence spectroscopy. PMID:23540203

  14. Reconsidering the quantitative analysis of organic carbon concentrations in size exclusion chromatography

    Microsoft Academic Search

    Ulrich Lankes; Margit B. Müller; Matthias Weber; Fritz H. Frimmel

    2009-01-01

    The evaluation of the molecular size distribution of natural organic matter (NOM) in aquatic environments via size exclusion chromatography (SEC) is important for the understanding of environmental processes such as nutrient cycling and pollutant transport as well as of technical water treatment processes. The use of organic carbon (OC) detectors has become popular in recent studies due to improved availability

  15. Characterization of DNA in cell culture supernatant by fluorescence-detection size-exclusion chromatography.

    PubMed

    Tan, Lihan; Yeo, Veronica; Yang, Yuansheng; Gagnon, Pete

    2015-05-01

    A fluorescence-detection size-exclusion chromatography (FSEC) method was developed to characterize DNA in cell culture supernatant. Samples stained with Picogreen were fractionated by size-exclusion chromatography (SEC) and monitored simultaneously by UV absorbance and fluorescence. SEC provided a size-characterization capability absent from bulk fluorescent assays, and was also free from interference from other fluorescent and UV-absorbing small-molecule cell culture components. FSEC revealed that DNA in mammalian cell culture supernatant exists mostly in the form of nucleosomal arrays. FSEC combined with agarose electrophoresis revealed spontaneous degradation of DNA in mammalian cell culture supernatant over a 30 day period at 4 °C: from arrays containing up to ~40 nucleosomes, down to arrays containing three or fewer nucleosomes. It also detected nucleosomal DNA in wheat, soy, and yeast hydrolysates commonly used to enhance cell culture productivity. PMID:25821116

  16. Size-exclusion liquid chromatography and capillary electrophoresis of pollen allergens

    Microsoft Academic Search

    V?ra Pacáková; Jitka Pechancová; Karel Štulík

    1996-01-01

    Allergens from the pollen of Phleum pratense, Dactylis glomerata. Arrhenatherum elatius, Secale cereale, Lolium perrene and Festuca sp. were analysed by size-exclusion chromatography (SEC) and capillary electrophoresis (CE). SEC was used for the determination of the molecular masses of main allergens. A CE method, using either 150 mmol\\/1 phosphoric acid (pH 1.8) or a micellar system consisting of 50 mmol\\/l

  17. Improved performance of protein separation by continuous annular chromatography in the size-exclusion mode

    Microsoft Academic Search

    Günter Iberer; Horst Schwinn; Djuro Josi?; Alois Jungbauer; Andrea Buchacher

    2001-01-01

    In size-exclusion chromatography (SEC), proteins and peptides are separated according to their molecular size in solution. SEC is especially useful as an effective fractionation step to separate a vast amount of impurities from the components of interest and\\/or as final step for the separation of purified proteins from their aggregates, in a so-called polishing step. However, the throughput in SEC

  18. Analysis of reduced monoclonal antibodies using size exclusion chromatography coupled with mass spectrometry

    Microsoft Academic Search

    Hongcheng Liu; Georgeen Gaza-Bulseco; Chris Chumsae

    2009-01-01

    Size-exclusion chromatography (SEC) has been widely used to detect antibody aggregates, monomer, and fragments. SEC coupled\\u000a to mass spectrometry has been reported to measure the molecular weights of antibody; antibody conjugates, and antibody light\\u000a chain and heavy chain. In this study, separation of antibody light chain and heavy chain by SEC and direct coupling to a mass\\u000a spectrometer was further

  19. Polystyrene-equivalent molecular weight versus true molecular weight in size-exclusion chromatography

    Microsoft Academic Search

    Miloš Netopil??k; Pavel Kratochv??l

    2003-01-01

    The evaluation of the size-exclusion chromatography (SEC) concentration elution curves by means of a calibration dependence obtained in a given SEC set for a polymer different from the polymer to be analyzed results in an error in the determination of both molecular weight and molecular-weight distribution (MWD). The problem is analyzed assuming the validity of the universal-calibration concept. The differences

  20. Synthesis of novel size exclusion chromatography support by surface initiated aqueous atom transfer radical polymerization.

    PubMed

    Coad, Bryan R; Kizhakkedathu, Jayachandran N; Haynes, Charles A; Brooks, Donald E

    2007-11-01

    We report the use of aqueous surface-initiated atom transfer radical polymerization (SI-ATRP) to grow polymer brushes from a "gigaporous" polymeric chromatography support for use as a novel size exclusion chromatography medium. Poly(N,N-dimethylacrylamide) (PDMA) was grown from hydrolyzable surface initiators via SI-ATRP catalyzed by 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA)/CuCl. Grafted polymer was characterized semiquantitatively by ATR-FTIR and also cleaved and quantitatively characterized for mass, molecular weight, and polydispersity via analytical SEC/MALLS. The synthesis provides control over graft density and allows the creation of dense brushes. Incorporation of negative surface charge was found to be crucial for improving the initiation efficiency. As polymer molecular weight and density could be controlled through reaction conditions, the resulting low-polydispersity grafted polymer brush medium is shown to be suitable for use as a customizable size exclusion chromatography medium for investigating the principals of entropic interaction chromatography. All packed media investigated showed size-dependent partitioning of solutes, even for low graft density systems. Increasing the molecular weight of the grafts allowed solutes more access to the volume fraction in the column available for partitioning. Compared to low graft density media, increased graft density caused eluted solute probes to be retained less within the column and allowed for greater size discrimination of probes whose molecular weights were less than 10(4) kDa. PMID:17924673

  1. Automated Precursor Ion Exclusion During LC-MS/MS Data Acquisition for Optimal Ion Identification

    NASA Astrophysics Data System (ADS)

    Zhang, Zhongqi

    2012-08-01

    Liquid chromatography-tandem mass spectrometry (LC-MS/MS) is widely used for characterizing multiple samples of complex mixtures with similar compositions. This article addresses a data acquisition strategy for collecting a maximal number of unique, high-quality MS/MS during LC-MS/MS analysis of multiple samples. Based on the concept that a component only needs to be identified once when analyzing multiple samples with similar compositions, an automated intersample data-dependent acquisition strategy was developed. The strategy is based on precursor ion exclusion (PIE) and is implemented in MassAnalyzer in an automated fashion for Thermo Scientific (San Jose, CA, USA) mass spectrometers. In this method, MassAnalyzer submits one sample at a time to the sample queue. After data acquisition of each sample, MassAnalyzer automatically analyzes the data to generate a PIE list based on the MS/MS precursor ions, merges this list with the list generated from previous runs, adds the list to the MS method file, and submits the next sample to the queue. The PIE list contains both m/z value and time window for each precursor ion, and is generated intelligently so that if an MS/MS is insufficient for identifying the peak of interest, it will be collected again near the top of the peak in the next run. Therefore, the strategy maximizes both quality and the number of unique MS/MS. When automated PIE was used to acquire LC-MS/MS data of an antibody tryptic digest and a soy hydrolysate sample, the number of identified ions increased by 52 % and 93 %, respectively, compared with data acquired without using PIE.

  2. 1.17972 Fractoprep Ion Exchange chromatography (IEX)

    E-print Network

    Lebendiker, Mario

    1.17972 Fractoprep® SO3 - Ion Exchange chromatography (IEX) Fractoprep® is a hydrophilic synthetic Sulfogroup (SO3)- Protein binding capacity ~ 100 mg lysozyme/ml of gel pH stability range pH 2 up to pH 14

  3. ANALYSIS OF FERRIC AND FERROUS IONS IN SOIL EXTRACTS BY ION CHROMATOGRAPHY

    EPA Science Inventory

    A method using ion chromatography (IC) for the analysis of ferrous (Fe 2+) and ferric (Fe 3+) ions in soil extracts has been developed. This method uses an ion exchange column with detection at 520 nm after post-column derivatization. Selectivity is achieved by using an anionic...

  4. Ion chromatography of cations using indirect photometric of fluorometric detection

    SciTech Connect

    Sherman, J.H.

    1987-01-01

    Copper(II) and cerium(III) were compared as mobile phase counter-ions with a strong cation exchange column for indirect photometric chromatography (IPC). Sample ion retention time was found to be dependent upon both counter-ion size and charge, as well as mobile phase ionic strength. Detection limits of all sample ions were found to be highly dependent on the molar absorptivity of the counter-ion at the wavelength of detection. At 254nm, a cerium(III) mobile phase provided detection limits at least 100 times lower than did a copper(II) mobile phase. The detection limit of sodium was about 4 ppb, corresponding to 3.5 pmoles, using a Ce(III) mobile phase. Cerium(III) was used as a mobile phase counter-ion with a strong cation exchange column using indirect fluorescence detection. Separation of the alkali metal ions along with the ammonium ion was achieved with baseline resolution. The detection limit of sodium was 3 ppb, corresponding to 2.6 pmoles. Separation and quantitation of sodium, ammonium, and potassium ions in diluted urine was straightforward. In contrast, using indirect UV detection, interference from the sample matrix was a problem. IPC using a cerium(III) mobile phase was used to determine sodium, potassium, magnesium, and calcium ions in milk and infant formulas. Separation was complete within 17 minutes. No interference from the sample matrix was noted. Good agreement between the IPC results and atomic absorption spectroscopy was found. Several complexes of chromium(III) were studied as mobile phase candidates for indirect photometric chromatography. A complex of tris(bipyridine)chromium(III) possessed the required spectral properties of an IPC counterion, but proved to be somewhat labile in either water or methanol but not acetonitrile.

  5. Size-exclusion chromatography for the determination of the boiling point distribution of high-boiling petroleum fractions.

    PubMed

    Boczkaj, Grzegorz; Przyjazny, Andrzej; Kami?ski, Marian

    2015-03-01

    The paper describes a new procedure for the determination of boiling point distribution of high-boiling petroleum fractions using size-exclusion chromatography with refractive index detection. Thus far, the determination of boiling range distribution by chromatography has been accomplished using simulated distillation with gas chromatography with flame ionization detection. This study revealed that in spite of substantial differences in the separation mechanism and the detection mode, the size-exclusion chromatography technique yields similar results for the determination of boiling point distribution compared with simulated distillation and novel empty column gas chromatography. The developed procedure using size-exclusion chromatography has a substantial applicability, especially for the determination of exact final boiling point values for high-boiling mixtures, for which a standard high-temperature simulated distillation would have to be used. In this case, the precision of final boiling point determination is low due to the high final temperatures of the gas chromatograph oven and an insufficient thermal stability of both the gas chromatography stationary phase and the sample. Additionally, the use of high-performance liquid chromatography detectors more sensitive than refractive index detection allows a lower detection limit for high-molar-mass aromatic compounds, and thus increases the sensitivity of final boiling point determination. PMID:25545251

  6. Liquid Chromatography in 1982.

    ERIC Educational Resources Information Center

    Freeman, David H.

    1982-01-01

    Reviews trends in liquid chromatography including apparatus, factors affecting efficient separation of a mixture (peak sharpness and speed), simplified problem-solving, adsorption, bonded phase chromatography, ion selectivity, and size exclusion. The current trend is to control chemical selectivity by the liquid phase. (Author/JN)

  7. Molar-Mass Characterization of Cationic Polymers for Gene Delivery by Aqueous Size-Exclusion Chromatography

    Microsoft Academic Search

    Xulin Jiang; Aschwin van der Horst; Mies J. van Steenbergen; Niels Akeroyd; Cornelus F. van Nostrum; Peter J. Schoenmakers; Wim E. Hennink

    2006-01-01

    \\u000a Purpose  This study was performed to develop a reliable aqueous size-exclusion chromatography (SEC) method to obtain the absolute molar\\u000a masses and distributions of various cationic polymers used in gene delivery.\\u000a \\u000a \\u000a \\u000a Methods  Water-soluble cationic [2-(dimethylamino) ethyl methacrylate] polymers (PDEs) with different molar masses and low polydispersities\\u000a were synthesized by living polymerization and these were used to optimize the SEC conditions. Online coupled multiangle

  8. Ion chromatography characterization of polysaccharides in ancient wall paintings

    Microsoft Academic Search

    Maria Perla Colombini; Alessio Ceccarini; Alessia Carmignani

    2002-01-01

    An analytical procedure for the characterisation of polysaccharides and the identification of plant gums in old polychrome samples is described. The procedure is based on hydrolysis with 2 M trifluoroacetic acid assisted by microwaves (20 min, 120°C, 500 W), clean-up of the hydrolysate by an ion-exchange resin, and analysis by high-performance anion-exchange chromatography with pulsed amperometric detection. Using this method

  9. Ion exclusion by sub-2-nm carbon nanotube pores

    PubMed Central

    Fornasiero, Francesco; Park, Hyung Gyu; Holt, Jason K.; Stadermann, Michael; Grigoropoulos, Costas P.; Noy, Aleksandr; Bakajin, Olgica

    2008-01-01

    Biological pores regulate the cellular traffic of a large variety of solutes, often with high selectivity and fast flow rates. These pores share several common structural features: the inner surface of the pore is frequently lined with hydrophobic residues, and the selectivity filter regions often contain charged functional groups. Hydrophobic, narrow-diameter carbon nanotubes can provide a simplified model of membrane channels by reproducing these critical features in a simpler and more robust platform. Previous studies demonstrated that carbon nanotube pores can support a water flux comparable to natural aquaporin channels. Here, we investigate ion transport through these pores using a sub-2-nm, aligned carbon nanotube membrane nanofluidic platform. To mimic the charged groups at the selectivity region, we introduce negatively charged groups at the opening of the carbon nanotubes by plasma treatment. Pressure-driven filtration experiments, coupled with capillary electrophoresis analysis of the permeate and feed, are used to quantify ion exclusion in these membranes as a function of solution ionic strength, pH, and ion valence. We show that carbon nanotube membranes exhibit significant ion exclusion that can be as high as 98% under certain conditions. Our results strongly support a Donnan-type rejection mechanism, dominated by electrostatic interactions between fixed membrane charges and mobile ions, whereas steric and hydrodynamic effects appear to be less important. PMID:18539773

  10. Quantifying vitamin K-dependent holoprotein compaction caused by differential ?-carboxylation using high-pressure size exclusion chromatography.

    PubMed

    Vanderslice, Nicholas C; Messer, Amanda S; Vadivel, Kanagasabai; Bajaj, S Paul; Phillips, Martin; Fatemi, Mostafa; Xu, Weijie; Velander, William H

    2015-06-15

    This study uses high-pressure size exclusion chromatography (HPSEC) to quantify divalent metal ion (X(2+))-induced compaction found in vitamin K-dependent (VKD) proteins. Multiple X(2+) binding sites formed by the presence of up to 12 ?-carboxyglutamic acid (Gla) residues are present in plasma-derived FIX (pd-FIX) and recombinant FIX (r-FIX). Analytical ultracentrifugation (AUC) was used to calibrate the Stokes radius (R) measured by HPSEC. A compaction of pd-FIX caused by the filling of Ca(2+) and Mg(2+) binding sites resulted in a 5 to 6% decrease in radius of hydration as observed by HPSEC. The filling of Ca(2+) sites resulted in greater compaction than for Mg(2+) alone where this effect was additive or greater when both ions were present at physiological levels. Less X(2+)-induced compaction was observed in r-FIX with lower Gla content populations, which enabled the separation of biologically active r-FIX species from inactive ones by HPSEC. HPSEC was sensitive to R changes of approximately 0.01nm that enabled the detection of FIX compaction that was likely cooperative in nature between lower avidity X(2+) sites of the Gla domain and higher avidity X(2+) sites of the epidermal growth factor 1 (EGF1)-like domain. PMID:25804408

  11. Chromatography.

    ERIC Educational Resources Information Center

    Brantley, L. Reed, Sr.; Demanche, Edna L.; Klemm, E. Barbara; Kyselka, Will; Phillips, Edwin A.; Pottenger, Francis M.; Yamamoto, Karen N.; Young, Donald B.

    This booklet presents some activities on chromatography. Directions for preparing leaf pigment extracts using alcohol are given, and paper chromatography and thin-layer chromatography are described as modifications of the basic principles of chromatography. (KHR)

  12. What can in situ ion chromatography offer for Mars exploration?

    PubMed

    Shelor, C Phillip; Dasgupta, Purnendu K; Aubrey, Andrew; Davila, Alfonso F; Lee, Michael C; McKay, Christopher P; Liu, Yan; Noell, Aaron C

    2014-07-01

    The successes of the Mars exploration program have led to our unprecedented knowledge of the geological, mineralogical, and elemental composition of the martian surface. To date, however, only one mission, the Phoenix lander, has specifically set out to determine the soluble chemistry of the martian surface. The surprising results, including the detection of perchlorate, demonstrated both the importance of performing soluble ion measurements and the need for improved instrumentation to unambiguously identify all the species present. Ion chromatography (IC) is the state-of-the-art technique for soluble ion analysis on Earth and would therefore be the ideal instrument to send to Mars. A flight IC system must necessarily be small, lightweight, low-power, and have low eluent consumption. We demonstrate here a breadboard system that addresses these issues by using capillary IC at low flow rates with an optimized eluent generator and suppressor. A mix of 12 ions known or plausible for the martian soil, including 4 (oxy)chlorine species, has been separated at flow rates ranging from 1 to 10 ?L/min, requiring as little as 200 psi at 1.0 ?L/min. This allowed the use of pneumatic displacement pumping from a pressurized aluminum eluent reservoir and the elimination of the high-pressure pump entirely (the single heaviest and most energy-intensive component). All ions could be separated and detected effectively from 0.5 to 100 ?M, even when millimolar concentrations of perchlorate were present in the same mixtures. PMID:24963874

  13. Size-exclusion liquid chromatography and capillary electrophoresis of pollen allergens.

    PubMed

    Pacáková, V; Pechancová, J; Stulík, K

    1996-05-31

    Allergens from the pollen of Phleum pratense, Dactylis glomerata. Arrhenatherum elatius, Secale cereale, Lolium perrene and Festuca sp. were analysed by size-exclusion chromatography (SEC) and capillary electrophoresis (CE). SEC was used for the determination of the molecular masses of main allergens. A CE method, using either 150 mmol/l phosphoric acid (pH 1.8) or a micellar system consisting of 50 mmol/l sodium dodecyl sulphate-20 mmol/l borate (pH 9.35), was developed as a rapid and efficient alternative to SEC, especially for process control of allergenic preparations. The results obtained by the two methods confirmed similarities in the structures of the studied pollen allergens. PMID:8798911

  14. High performance size exclusion chromatography (IX) bulk and component analysis of silanol groups in polydimethylsiloxanes

    SciTech Connect

    Kohn, E.

    1985-01-01

    Methods for the bulk and molecular weight component analysis of hydroxyl groups attached to silicon in polydimethylsiloxanes of the Sylgard type have been developed. The infrared (ir) absorbance band of the silanol adduct produced by hydrogen bonding with 1,4-dioxane is used. The determination of hydroxyl content as a function of molecular weight employs an on-line size exclusion chromatography-infrared (SEC-IR) technique. Interference by vinyl or phenyl groups in the sample or by traces of water in the solvent was negligible, but water or compounds containing other types of hydroxyl groups interfered. Sensitivity of the method is about 10 ..mu..g of the silanol, as OH in the polydimethylsiloxane. Primary calibration was by proton nuclear magnetic resonance (PNMR) at a high concentration of hydroxyl groups.

  15. Fluorescence-Detectino Size-Exclusion Chromatography for Precrystallization Screening of Integral Membrane Proteins

    SciTech Connect

    Kawate,T.; Gouaux, E.

    2006-01-01

    Formation of well-ordered crystals of membrane proteins is a bottleneck for structure determination by X-ray crystallography. Nevertheless, one can increase the probability of successful crystallization by precrystallization screening, a process by which one analyzes the monodispersity and stability of the protein-detergent complex. Traditionally, this has required microgram to milligram quantities of purified protein and a concomitant investment of time and resources. Here, we describe a rapid and efficient precrystallization screening strategy in which the target protein is covalently fused to green fluorescent protein (GFP) and the resulting unpurified protein is analyzed by fluorescence-detection size-exclusion chromatography (FSEC). This strategy requires only nanogram quantities of unpurified protein and allows one to evaluate localization and expression level, the degree of monodispersity, and the approximate molecular mass. We show the application of this precrystallization screening to four membrane proteins derived from prokaryotic or eukaryotic organisms.

  16. Determination of sulphite in wines using suppressed ion chromatography.

    PubMed

    Yoshikawa, Kenji; Uekusa, Yuki; Sakuragawa, Akio

    2015-05-01

    Suppressed ion chromatography with the use of a conductivity detector was developed for the determination of sulphite ions in wine samples. When a mixed solution of sodium carbonate, sodium bicarbonate, and acetone was used as the mobile phase, simultaneous determination of eight inorganic anions (i.e., fluoride, chloride, nitrite, nitrate, sulphite, phosphate, sulphate, and thiosulphate) was completed in approximately 25 min. Linearity, reproducibility, and detection limits were determined for the proposed method. In the case of sulphite detection, a linear calibration curve with a good correlation coefficient of 0.9992 was obtained from the peak height of sulphite with a relative standard deviation (n = 6) 1.48%. In addition, the detection limit of sulphite was 0.27 mg/L at a signal-to-noise ratio of 3. Further, the developed method was applied for the determination of sulphite contained in several wine samples. PMID:25529696

  17. Determination of counter-ions in synthetic peptides by ion chromatography, capillary isotachophoresis and capillary electrophoresis.

    PubMed

    Mrozik, Wojciech; Markowska, Aleksandra; Guzik, Lukasz; Kraska, Bart?omiej; Kamysz, Wojciech

    2012-03-01

    The utility of three various analytical techniques [ion chromatography (IC), capillary electrophoresis (CE) and isotachophoresis (ITP)] was tested in the determination of counter-ions in synthetic peptides. The analyzed ions were acetates, trifluoroacetates and chlorides. IC provided the best results; CE, except limit of detection and limit of quantification, exhibited the comparable results. ITP was classified as the less useful because of the problem with the determination of the chloride ions. Nevertheless, all the three techniques were able to analyze trifluoroacetates and acetates ions with satisfactory results. Except analytical methods, three procedures using hydrochloric acid (HCl) (at two different concentrations) and acetic acid as sample solvents processed by lyophilization were tested. It has been found that the lyophilization not only by HCl but also by acetic acid is a simple and cheap procedure for removal of toxic trifluoroacetic counter-ions from peptides on satisfactory levels. PMID:22252914

  18. Analysis of anions in aqueous samples by ion chromatography and capillary electrophoresis

    Microsoft Academic Search

    S. L. Tamisier-Karolak; I. Le Potier; O. Barlet; M. Czok

    1999-01-01

    The object of this study is the comparison of two methods for the quantitative analysis of anions in aqueous samples: ion chromatography with conductimetric detection, and capillary zone electrophoresis with indirect photometric detection. The comparison includes modeling of experimental peaks as well as statistical validation criteria according to the recommendations of the International Conference on Harmonisation. In ion chromatography, peak

  19. Ion Exclusion by Sub 2-nm Carbon Nanotube Pores

    SciTech Connect

    Fornasiero, F; Park, H G; Holt, J K; Stadermann, M; Grigoropoulos, C P; Noy, A; Bakajin, O

    2008-04-09

    Carbon nanotubes offer an outstanding platform for studying molecular transport at nanoscale, and have become promising materials for nanofluidics and membrane technology due to their unique combination of physical, chemical, mechanical, and electronic properties. In particular, both simulations and experiments have proved that fluid flow through carbon nanotubes of nanometer size diameter is exceptionally fast compared to what continuum hydrodynamic theories would predict when applied on this length scale, and also, compared to conventional membranes with pores of similar size, such as zeolites. For a variety of applications such as separation technology, molecular sensing, drug delivery, and biomimetics, selectivity is required together with fast flow. In particular, for water desalination, coupling the enhancement of the water flux with selective ion transport could drastically reduce the cost of brackish and seawater desalting. In this work, we study the ion selectivity of membranes made of aligned double-walled carbon nanotubes with sub-2 nm diameter. Negatively charged groups are introduced at the opening of the carbon nanotubes by oxygen plasma treatment. Reverse osmosis experiments coupled with capillary electrophoresis analysis of permeate and feed show significant anion and cation rejection. Ion exclusion declines by increasing ionic strength (concentration) of the feed and by lowering solution pH; also, the highest rejection is observed for the A{sub m}{sup Z{sub A}} C{sub n}{sup Z{sub C}} salts (A=anion, C=cation, z= valence) with the greatest Z{sub A}/Z{sub C} ratio. Our results strongly support a Donnan-type rejection mechanism, dominated by electrostatic interactions between fixed membrane charges and mobile ions, while steric and hydrodynamic effects appear to be less important. Comparison with commercial nanofiltration membranes for water softening reveals that our carbon nanotube membranes provides far superior water fluxes for similar ion rejection capabilities.

  20. Assay of uranium in the presence of various interfering ions using ion pair liquid chromatography

    SciTech Connect

    Riaz, M.; Butt, S.B.; Haq, E.U. (Nuclear Chemistry Div. PINSTECH, Islamabad (Pakistan))

    1993-01-01

    A sensitive and specific method for uranium(6) determination using reverse phase ion-pair high performance liquid chromatography with UV detector has been developed. The developed method has been applied for the determination of uranium in a synthetic sample containing most of the interfering ions. Except iron most of the elements and anion which often interfere in uranium assay do not interfere in the present method. Interference of iron is masked by addition of 5mM/1 EDTA solution to the sample.

  1. Size exclusion chromatography for analyses of fibroin in silk: optimization of sampling and separation conditions

    NASA Astrophysics Data System (ADS)

    Pawcenis, Dominika; Koperska, Monika A.; Milczarek, Jakub M.; ?ojewski, Tomasz; ?ojewska, Joanna

    2014-02-01

    A direct goal of this paper was to improve the methods of sample preparation and separation for analyses of fibroin polypeptide with the use of size exclusion chromatography (SEC). The motivation for the study arises from our interest in natural polymers included in historic textile and paper artifacts, and is a logical response to the urgent need for developing rationale-based methods for materials conservation. The first step is to develop a reliable analytical tool which would give insight into fibroin structure and its changes caused by both natural and artificial ageing. To investigate the influence of preparation conditions, two sets of artificially aged samples were prepared (with and without NaCl in sample solution) and measured by the means of SEC with multi angle laser light scattering detector. It was shown that dialysis of fibroin dissolved in LiBr solution allows removal of the salt which destroys stacks chromatographic columns and prevents reproducible analyses. Salt rich (NaCl) water solutions of fibroin improved the quality of chromatograms.

  2. Prediction of the viscosity radius and the size exclusion chromatography behavior of PEGylated proteins.

    PubMed

    Fee, Conan J; Van Alstine, James M

    2004-01-01

    Size exclusion chromatography (SEC) was used to determine the viscosity radii of equivalent spheres for proteins covalently grafted with poly(ethylene glycol) (PEG). The viscosity radius of such PEGylated proteins was found to depend on the molecular weight of the native protein and the total weight of grafted PEG but not on PEG molecular weight, or PEG-to-protein molar grafting ratio. Results suggest grafted PEG's form a dynamic layer over the surface of proteins. The geometry of this layer results in a surface area-to-volume ratio approximately equal to that of a randomly coiled PEG molecule of equivalent total molecular weight. Two simple methods are given to predict the viscosity radius of PEGylated proteins. Both methods accurately predicted (3% absolute error) the viscosity radii of various PEG-proteins produced using three native proteins, alpha-lactalbumin (14.2 kDa MW), beta-lactoglobulin dimer (37.4 kDa MW), and bovine serum albumin (66.7 kDa MW), three PEG reagents (2400, 5600, and 22500 MW), and molar grafting ratios of 0 to 8. Accurate viscosity radius prediction allows calculation of the distribution coefficient, K(av), for PEG-proteins in SEC. The suitability of a given SEC step for the analytical or preparative fractionation of different PEGylated protein mixtures may therefore be assessed mathematically. The methods and results offer insight to several factors related to the production, purification, and uses of PEGylated proteins. PMID:15546197

  3. Studying Arsenite-Humic Acid Complexation Using Size Exclusion Chromatography-Inductively Coupled Plasma Mass Spectrometry

    PubMed Central

    Liu, Guangliang; Cai, Yong

    2012-01-01

    Arsenic (As) can form complexes with dissolved organic matter (DOM), which affects the fate of arsenic in waste sites and natural environments. It remains a challenge to analyze DOM-bound As, in particular by using a direct chromatographic separation method. Size exclusion chromatography (SEC) hyphenated with UV spectrophotometer and inductively coupled plasma mass spectrometry (ICP-MS) was developed to characterize the complexation of arsenite (AsIII) with DOM. This SEC-UV-ICP-MS method is able to differentiate AsIII-DOM complexes from free As species and has the advantage of direct determination of both free and DOM-bound AsIII through mild separation. The suitability of this method for studying AsIII-DOM complexation was demonstrated by its application, in combination with the Scatchard plot and nonlinear regression of ligand binding model, for characterizing AsIII complexation with humic acid (HA) in the absence or presence of natural sand. The results suggest that, consistent with polyelectrolytic nature of HA, the AsIII-HA complexation should be accounted for by multiple classes of binding sites. By loosely classifying the binding sites into strong (S1) and weak (S2) sites, the apparent stability constants (Ks) of the resulting As-DOM complexes were calculated as log Ks1 = 6.5–7.1 while log Ks2 = 4.7–5.0. PMID:22664255

  4. Analysis of reduced monoclonal antibodies using size exclusion chromatography coupled with mass spectrometry

    NASA Astrophysics Data System (ADS)

    Liu, Hongcheng; Gaza-Bulseco, Georgeen; Chumsae, Chris

    2009-12-01

    Size-exclusion chromatography (SEC) has been widely used to detect antibody aggregates, monomer, and fragments. SEC coupled to mass spectrometry has been reported to measure the molecular weights of antibody; antibody conjugates, and antibody light chain and heavy chain. In this study, separation of antibody light chain and heavy chain by SEC and direct coupling to a mass spectrometer was further studied. It was determined that employing mobile phases containing acetonitrile, trifluoroacetic acid, and formic acid allowed the separation of antibody light chain and heavy chain after reduction by SEC. In addition, this mobile phase allowed the coupling of SEC to a mass spectrometer to obtain a direct molecular weight measurement. The application of the SEC-MS method was demonstrated by the separation of the light chain and the heavy chain of multiple recombinant monoclonal antibodies. In addition, separation of a thioether linked light chain and heavy chain from the free light chain and the free heavy chain of a recombinant monoclonal antibody after reduction was also achieved. This optimized method provided a separation of antibody light chain and heavy chain based on size and allowed a direct measurement of molecular weights by mass spectrometry. In addition, this method may help to identify peaks eluting from SEC column directly.

  5. Estimation of the band broadening parameters in single detection size-exclusion chromatography: A comparative study of various column combinations

    Microsoft Academic Search

    Irene Schnöll-Bitai; Jorge Vega; Christoph Mader

    2007-01-01

    Alternative approaches for the determination of band broadening in size-exclusion chromatography based on the use of exponentially modified Gaussian (EMG) functions were used to experimentally investigate the performance of two different column sets. In both cases, the columns were combined in order to cover the complete fractionation range (from 103 to 5×106gmol?1), which is of interest in many applications. When

  6. Analysis of aggregates of human immunoglobulin G using size-exclusion chromatography, static and dynamic light scattering

    Microsoft Academic Search

    K. Ahrer; A. Buchacher; G. Iberer; D. Josic; A. Jungbauer

    2003-01-01

    Large aggregates (Mr: 106–107 g\\/mol) of human immunoglobulins are present in extremely small concentrations in IgG preparations (<0.1%). Traces of large protein aggregates cannot be determined by conventional size-exclusion chromatography (SEC) using UV detection due to limitations in sensitivity. The conventional analysis of IgG by SEC is limited to dimers and oligomers. Using light scattering it is possible to determine

  7. Liquid chromatography of polymer mixtures applying a combination of exclusion and full adsorption mechanisms: 2. Eluent switching approach

    Microsoft Academic Search

    Tatyana Prudskova

    1995-01-01

    The molar mass and molar mass distribution of particular components of a polymer mixture can be determined by a combination of size exclusion chromatography (s.e.c.) and full adsorption\\/desorption (f.a.d.) modes. One component of a polymer mixture is retained on the surface of an appropriate sorbent using an appropriate eluent while another component is chromatographed in the conventional s.e.c. mode. In

  8. Observation of Absence of Mechanical Degradation of High Molecular Weight Polystyrenes During Elution Through a Column in Size Exclusion Chromatography

    Microsoft Academic Search

    Masahide Nakamura; Yurika Ofusa; Sadao Mori

    1996-01-01

    Size exclusion chromatography of several polystyrene (PS) standards of a narrow molecular weight (MW) distribution was performed with an on-line light scattering detector (MALLS) using Shodex SEC column KF 806L packed with PS gel packings. Tetrahydrofuran was used as the mobile phase and the flow rate was 1.0 mL\\/min. Mechanical degradation of the sample PS was not observed even the

  9. Determination of major element chemistry in terrestrial waters from Antarctica by ion chromatography

    Microsoft Academic Search

    K. A Welch; W. B Lyons; E Graham; K Neumann; J. M Thomas; D Mikesell

    1996-01-01

    As part of the new Long Term Ecological Research (LTER) project in the McMurdo Dry Valleys of Antarctica, a systematic aqueous geochemical sampling program has been undertaken. A series of terrestrial water samples have been collected and analyzed for major ion chemistry by ion chromatography. The concentrations of ions cover a wide range of total dissolved solids (TDS) from relatively

  10. Universal theoretical moment expressions for elution and frontal chromatography of pellicular ion exchange resins

    Microsoft Academic Search

    Yang Gengliang; Hu Zhide

    1996-01-01

    In this paper, theoretical moment expressions for elution and frontal chromatographies are derived when the packing material in a column is pellicular ion exchange resin. From the retention time and the height equivalent to a theoretical plate (HEPT) obtained, the advantages of the pellicular ion exchange resin are discussed by comparing with the conventional ion exchange resin bead.

  11. Determination of Cyanogenic Compounds in Edible Plants by Ion Chromatography

    PubMed Central

    Cho, Hye-Jeon; Do, Byung-Kyung; Shim, Soon-Mi; Lee, Dong-Ha; Nah, Ahn-Hee; Choi, Youn-Ju; Lee, Sook-Yeon

    2013-01-01

    Cyanogenic glycosides are HCN-producing phytotoxins; HCN is a powerful and a rapidly acting poison. It is not difficult to find plants containing these compounds in the food supply and/or in medicinal herb collections. The objective of this study was to investigate the distribution of total cyanide in nine genera (Dolichos, Ginkgo, Hordeum, Linum, Phaseolus, Prunus, Phyllostachys, Phytolacca, and Portulaca) of edible plants and the effect of the processing on cyanide concentration. Total cyanide content was measured by ion chromatography following acid hydrolysis and distillation. Kernels of Prunus genus are used medicinally, but they possess the highest level of total cyanide of up to 2259.81 CN?/g dry weight. Trace amounts of cyanogenic compounds were detected in foodstuffs such as mungbeans and bamboo shoots. Currently, except for the WHO guideline for cassava, there is no global standard for the allowed amount of cyanogenic compounds in foodstuffs. However, our data emphasize the need for the guidelines if plants containing cyanogenic glycosidesare to be developed as dietary supplements. PMID:24278641

  12. Analysis of anions in beer using ion chromatography.

    PubMed

    Bruce, Jonathan

    2002-01-01

    The majority of anions found in beer are a consequence of impurities derived from the water used during the brewing process. The process of beer manufacture consists of malting, brewing and fermentation followed by maturation before filtration and finally storage. Strict quality control is required because the presence of certain anions outside strictly defined tolerance limits can affect the flavour characteristics of the finished product. The anions present were quantified using the technique of ion chromatography with the Metrohm modular system following sample preparation. The analysis produced a result of the order 200 mg l(-1) for chloride, phosphate and sulphate and around 20 mg l(-1) for nitrate. If the chloride level exceeds 250 mg l(-1), then the sweetness of the beer is enhanced, but yeast flocculation can be hindered. An excess of sulphate can give a sharp, dry edge to hopped beers and excessive amounts of nitrate have been found to harm the yeast metabolism after conversion to the nitrite form. As water is a primary ingredient within beer, its quality and type is a fundamental factor in establishing many of the distinctive regional beers that can be found in the United Kingdom and is thus monitored carefully. PMID:18924733

  13. Thin layer chromatography-ion mobility spectrometry (TLC-IMS).

    PubMed

    Ilbeigi, Vahideh; Tabrizchi, Mahmoud

    2015-01-01

    Ion mobility spectrometry (IMS) is a fast and sensitive analytical method which operates at the atmospheric pressure. To enhance the capability of IMS for the analysis of mixtures, it is often used with preseparation techniques, such as GC or HPLC. Here, we report for the first time the coupling of the thin-layer chromatography and IMS. A variety of coupling schemes were tried that included direct electrospray from the TLC strip tip, indirect electrospray from a needle connected to the TLC strip, introducing the moving solvent into the injection port, and, the simplest way, offline introduction of scratched or cut pieces of strips into the IMS injection port. In this study a special solvent tank was designed and the TLC strip was mounted horizontally where the solvent would flow down. A very small funnel right below the TLC tip collected the solvent and transferred it to a needle via a capillary tubing. Using the TLC-ESI-IMS technique, acceptable separations were achieved for two component mixtures of morphine-papaverine and acridine-papaverine. A special injection port was designed to host the pieces cut off the TLC. The method was successfully used to identify each spot on the TLC by IMS in a few seconds. PMID:25419999

  14. Elucidating the redox cycle of environmental phosphorus using ion chromatography.

    PubMed

    Pech, Herbe; Vazquez, Maria G; Van Buren, Jean; Shi, Lixin; Ivey, Michelle M; Salmassi, Tina M; Pasek, Matthew A; Foster, Krishna L

    2011-09-01

    Historically, it was assumed that reactive, inorganic phosphorus present in pristine environments was solely in the form of orthophosphate. However, this assumption contradicts theories of biogenesis and the observed metabolic behavior of select microorganisms. This paper discusses the role of ion chromatography (IC) in elucidating the oxidation-reduction cycle of environmental phosphorus. These methods employ suppressed-IC, coupled with tandem conductivity and electrospray mass spectrometry detectors to identify and quantify phosphorus oxyanions in natural water, synthetic cosmochemical, and biological samples. These techniques have been used to detect phosphite and orthophosphate in geothermal hot springs. Hypophosphite, phosphite, and orthophosphate have been detected in synthetic schreibersite corrosion samples, and termite extract supernatant. Synthetic schreibersite corrosion samples were also analyzed for two poly-phosphorus compounds, hypophosphate and pyrophosphate, and results show these samples did not contain concentrations above the 1.3 and 2.0 ?M respective 3? limit of detection. These methods are readily adaptable to a variety of matrices, and contribute to the elucidation of the oxidation-reduction cycle of phosphorus oxyanions in the environment. In contrast to most studies, these techniques have been used to show that phosphorus actively participates in redox processes in both the biological and geological world. PMID:21859529

  15. Determination of cyanogenic compounds in edible plants by ion chromatography.

    PubMed

    Cho, Hye-Jeon; Do, Byung-Kyung; Shim, Soon-Mi; Kwon, Hoonjeong; Lee, Dong-Ha; Nah, Ahn-Hee; Choi, Youn-Ju; Lee, Sook-Yeon

    2013-06-01

    Cyanogenic glycosides are HCN-producing phytotoxins; HCN is a powerful and a rapidly acting poison. It is not difficult to find plants containing these compounds in the food supply and/or in medicinal herb collections. The objective of this study was to investigate the distribution of total cyanide in nine genera (Dolichos, Ginkgo, Hordeum, Linum, Phaseolus, Prunus, Phyllostachys, Phytolacca, and Portulaca) of edible plants and the effect of the processing on cyanide concentration. Total cyanide content was measured by ion chromatography following acid hydrolysis and distillation. Kernels of Prunus genus are used medicinally, but they possess the highest level of total cyanide of up to 2259.81 CN(-)/g dry weight. Trace amounts of cyanogenic compounds were detected in foodstuffs such as mungbeans and bamboo shoots. Currently, except for the WHO guideline for cassava, there is no global standard for the allowed amount of cyanogenic compounds in foodstuffs. However, our data emphasize the need for the guidelines if plants containing cyanogenic glycosidesare to be developed as dietary supplements. PMID:24278641

  16. Speciation of trace elements in proteins in human and bovine serum by size exclusion chromatography and inductively coupled plasma-mass spectrometry with a magnetic sector mass spectrometer.

    PubMed

    Wang, J; Houk, R S; Dreessen, D; Wiederin, D R

    1999-10-01

    Proteins are separated by size exclusion chromatography while atomic ions from the inorganic elements are detected on-line by inductively coupled plasma-mass spectrometry. A double focusing mass analyzer provides very high sensitivity, low background, and sufficient spectral resolution to separate the atomic ions of interest from most polyatomic ions at the same nominal m/z value. The chromatograms show the distribution of the elements of interest between protein-bound and free fractions and provide the approximate molecular weights of those protein fractions that contain the elements monitored. The distribution of various elements, including V, Mo, Fe, Co, Mn, and lanthanides, in human or bovine serum samples are shown. Alkali metals and Tl are present primarily as free metal ions and are not bound to proteins. Inorganic elements spiked into the serum samples can be followed into various proteins. EDTA does not remove Fe, Pb, Sn, or Th from the proteins but does extract Mn from some proteins. Procedures for determining the effects of breaking disulfide linkages on the metal binding characteristics of proteins are also described. PMID:10550683

  17. Improvements of a combined size exclusion chromatography and solid phase extraction approach for the clean-up of marine sediment samples for trace analysis of pesticides

    Microsoft Academic Search

    K. Bester; Heinrich Hühnerfuss

    1997-01-01

    Two methods based on gel permeation chromatography (GPC) [size exclusion chromatography] for the analysis of traces (ng\\/kg)\\u000a of nitrogen and phosphorus containing pesticides (like triazines or phosphothionates) from marine sediment samples are compared:\\u000a A macro GPC with Biobeads SX-3 and a chromatography on a high-performance (HP-GPC) column with UV-detection. Results for eight\\u000a triazine herbicides, two triazine metabolites, the phenylurea derivative

  18. Study of the degradation of gelatin in paper upon aging using aqueous size-exclusion chromatography.

    PubMed

    Dupont, Anne-Laurence

    2002-03-15

    We studied the aging behaviour of gelatin used to size paper. Thus far, research on the aging of paper has largely ignored the sizing agent. Degradation of the protein was characterised and the impact of paper components, such as cellulose, and aluminium potassium sulphate was evaluated. Whatman No. 1 filter papers sized with two types of gelatins (A and B) were prepared as model samples. Commercially sized modern papers (Arches) were also studied in order to compare laboratory samples with real artist papers. Both types of papers were artificially aged (80 degrees C, 50% relative humidity for 35 and 94 days). Historic papers were included in the study in order to compare artificially aged with naturally aged gelatin. The aqueous extracts from the papers were characterised by aqueous size-exclusion chromatography (SEC) using four PL-Aquagel-OH columns and UV photodiode array detection at 220, 254 and 280 nm. Results showed that gelatin undergoes hydrolysis upon aging, type A gelatin showing a faster degradation rate than type B. The result was an increase in the lower-molar-mass fractions, under 50,000 g mol(-1), and especially in a characteristic fraction with a peak molecular mass (MP) of 14,000 g mol(-1). A significant decrease in the extraction yields of alpha-, beta- and gamma-chains occurred after aging. This was attributed to crosslinking, leading to the formation of less-soluble polypeptides with very high molar mass (>800,000 g mol(-1)) Less than 10% alum had no impact on the degradation rate; higher alum contents accelerated hydrolysis reactions. PMID:11990984

  19. Size-exclusion chromatography in the measurements of concentration and molecular weight of some EOR polymers

    SciTech Connect

    Hunt, J.A.; Young, T.S.; Green, D.W.; Willhite, G.P.

    1988-08-01

    Procedures that involve the use of size exclusion chromatography (SEC) for the measurement of concentration and weight-averaged molecular weight, M-bar/sub w/, of some EOR polymers were developed and found to give improved detectability, accuracy, and/or efficiency. The separation of polymer from low-molecular-weight impurities by size allows unambiguous detection of polymer properties such as concentration and M-bar/sub w/. A combination of an SEC column of a pore size small enough to exclude the polymer totally and a mobile phase of ionic strength of 1.5 was found suitable for the separation of polyacrylamide, partially hydrolyzed polyacrylamide, cationic polyacrylamide derivative, and xanthan polysaccharide from impurities. Concentration detection of the separated polymer sample with a variable-wavelength ultraviolet (UV) detector was found to give superior detectability over detection by refractive index difference. A wavelength of 214 nm (2,140 A) was used for the detection of these polymers on the basis of the spectra of samples purified by dialysis. With the active polymer assay determined by reprecipitation into a nonsolvent, the detection limit by UV was determined to be <0.1 ..mu..g/cm/sup 3/ for polyacrylamide and a cationic polyacrylamide derivative, <0.2 ..mu..g/cm/sup 3/ for partially hydrolyzed polyacrylamide, and <0.7 ..mu..g/cm/sup 3/ for a xanthan polysaccharide. The linear calibration range was up to 500 ..mu..g/cm/sup 3/. The precision of the concentration measurement was better than 4% for polyacrylamide and its derivative and 5% for polysaccharide at a 95% confidence level.

  20. Size-exclusion chromatography-based enrichment of extracellular vesicles from urine samples

    PubMed Central

    Lozano-Ramos, Inés; Bancu, Ioana; Oliveira-Tercero, Anna; Armengol, María Pilar; Menezes-Neto, Armando; Del Portillo, Hernando A.; Lauzurica-Valdemoros, Ricardo; Borràs, Francesc E.

    2015-01-01

    Renal biopsy is the gold-standard procedure to diagnose most of renal pathologies. However, this invasive method is of limited repeatability and often describes an irreversible renal damage. Urine is an easily accessible fluid and urinary extracellular vesicles (EVs) may be ideal to describe new biomarkers associated with renal pathologies. Several methods to enrich EVs have been described. Most of them contain a mixture of proteins, lipoproteins and cell debris that may be masking relevant biomarkers. Here, we evaluated size-exclusion chromatography (SEC) as a suitable method to isolate urinary EVs. Following a conventional centrifugation to eliminate cell debris and apoptotic bodies, urine samples were concentrated using ultrafiltration and loaded on a SEC column. Collected fractions were analysed by protein content and flow cytometry to determine the presence of tetraspanin markers (CD63 and CD9). The highest tetraspanin content was routinely detected in fractions well before the bulk of proteins eluted. These tetraspanin-peak fractions were analysed by cryo-electron microscopy (cryo-EM) and nanoparticle tracking analysis revealing the presence of EVs. When analysed by sodium dodecyl sulphate–polyacrylamide gel electrophoresis, tetraspanin-peak fractions from urine concentrated samples contained multiple bands but the main urine proteins (such as Tamm–Horsfall protein) were absent. Furthermore, a preliminary proteomic study of these fractions revealed the presence of EV-related proteins, suggesting their enrichment in concentrated samples. In addition, RNA profiling also showed the presence of vesicular small RNA species. To summarize, our results demonstrated that concentrated urine followed by SEC is a suitable option to isolate EVs with low presence of soluble contaminants. This methodology could permit more accurate analyses of EV-related biomarkers when further characterized by -omics technologies compared with other approaches. PMID:26025625

  1. Single-step isolation of extracellular vesicles by size-exclusion chromatography

    PubMed Central

    Böing, Anita N.; van der Pol, Edwin; Grootemaat, Anita E.; Coumans, Frank A. W.; Sturk, Auguste; Nieuwland, Rienk

    2014-01-01

    Background Isolation of extracellular vesicles from plasma is a challenge due to the presence of proteins and lipoproteins. Isolation of vesicles using differential centrifugation or density-gradient ultracentrifugation results in co-isolation of contaminants such as protein aggregates and incomplete separation of vesicles from lipoproteins, respectively. Aim To develop a single-step protocol to isolate vesicles from human body fluids. Methods Platelet-free supernatant, derived from platelet concentrates, was loaded on a sepharose CL-2B column to perform size-exclusion chromatography (SEC; n=3). Fractions were collected and analysed by nanoparticle tracking analysis, resistive pulse sensing, flow cytometry and transmission electron microscopy. The concentrations of high-density lipoprotein cholesterol (HDL) and protein were measured in each fraction. Results Fractions 9–12 contained the highest concentrations of particles larger than 70 nm and platelet-derived vesicles (46%±6 and 61%±2 of totals present in all collected fractions, respectively), but less than 5% of HDL and less than 1% of protein (4.8%±1 and 0.65%±0.3, respectively). HDL was present mainly in fractions 18–20 (32%±2 of total), and protein in fractions 19–21 (36%±2 of total). Compared to the starting material, recovery of platelet-derived vesicles was 43%±23 in fractions 9–12, with an 8-fold and 70-fold enrichment compared to HDL and protein. Conclusions SEC efficiently isolates extracellular vesicles with a diameter larger than 70 nm from platelet-free supernatant of platelet concentrates. Application SEC will improve studies on the dimensional, structural and functional properties of extracellular vesicles. PMID:25279113

  2. Size exclusion chromatography (XIII): Identification and quantitation of silicon hydride containing oligomeric components of Sylgard prepolymers. [Polydimethylsiloxane

    SciTech Connect

    Kohn, E.; Chisum, M.E.; Moore, K.L.

    1987-12-01

    Methods for the identification and quantitation of oligomeric, silicon hydride (SiH), containing components of Sylgard prepolymers (polydimethylsiloxane: PDMS) have been developed. They employ a combination of size exclusion chromatography (SEC), with infrared (ir) and differential refractometer (DR) detection and gas chromatography/mass spectrometry (GC/MS) verification. The identified oligomers were present at about 20% of total prepolymer and contained from one to six SiH linkages per molecule. Such lower molecular weight oligomers may contribute to the vapor pressure of resins prepared from the prepolymers since they may contain a significant number of molecules which have only one or two SiH groups and are not capable of forming large polymeric structures. 5 refs., 8 figs., 2 tabs.

  3. ANALYSIS OF NITRITE IN NO2 DIFFUSION TUBES USING ION CHROMATOGRAPHY

    EPA Science Inventory

    An analytical method was developed for the analysis of the NO2 collected by a passive diffusion controlled atmospheric sampling device. The method measured the total amount of nitrite ion using ion chromatography. The precision obtained under field conditions, defined as twice th...

  4. Application of the zeta potential for stationary phase characterization in ion chromatography.

    PubMed

    Buszewski, Bogus?aw; Ja?kowska, Magdalena; Bocian, Szymon; Dziubakiewicz, Ewelina

    2013-01-01

    Two series of homemade stationary bonded phases for ion chromatography were investigated according to their zeta potential. One set of dendrimer anion exchanger was synthesized on the polymer support whereas the second material was prepared on the silica gel. The zeta potential data in water environment as well as buffered water solution were obtained. The influence of the length of anion-exchanger chains, the type of the support of the modified surface, and charge distribution on these data was investigated. Additionally, the zeta potential was correlated with retention factor of inorganic ions to describe their influence on the retention mechanism in ion chromatography. PMID:23292851

  5. Chromatography

    NSDL National Science Digital Library

    WGBH Boston

    2002-01-01

    In this activity, explore chromatography and the various colors that make up the ink in markers. Use this activity to investigate cohesion and adhesion. The online version of this activity is set up so that learners solve a mystery.

  6. [Determination of hydrazine ion in explosion dust of liquid explosive by ion chromatography].

    PubMed

    Wang, Yong; Geng, Qing; Zuo, Yuexian; Zhou, Xinwen; Lian, Hongzhen; Pan, Guangwen

    2013-09-01

    A method for the determination of hydrazine ion in explosion dust of liquid explosive has been established by ion chromatography. The hydrazine ion in an explosion dust sample was extracted with deionized water by sonification and centrifugation. The large molecules and solid particles in supernatant were removed by an OnGuard II RP column and a 0.22 microm filtration membrane, respectively. The filtrate was separated on an IonPac CS-12A column with isocratic elution of 5 mmol/L methanesulfonic acid (MSA). Then 0.1 mol/L NaOH solution was post-column added and the resultant solution was detected by an ampere detector with golden electrode. The results showed that, the calibration curve was linear in the range of 0.02 - 2.0 mg/L with a correlation coefficient (r2 ) of 0.999 7. The limits of detection (LOD, S/N = 3) and quantification (LOQ, S/N = 10) of hydrazine were 5.0 microg/L and 16.6 microg/L, respectively. The recoveries ranged between 95.4% and 99.1% with the relative standard deviations (RSDs, n = 5) of 2.1% - 3.3%. The hydrazine content in a real explosion dust sample of liquid explosive was 10.3 mg/kg by this method. The method is simple, accurate, and suitable for the quantitative detection of hydrazine ions in explosion dust of liquid explosive, and the method can meet the needs of the criminal evidence identification work. PMID:24392633

  7. DETERMINATION OF TRACE ANIONS IN WATER BY MULTIDIMENSIONAL ION CHROMATOGRAPHY

    EPA Science Inventory

    Selenate, selenite, and arsenate ions were separated from the major anions chloride, nitrate, and sulfate in drinking water, surface water, and groundwater sources by collecting a selected portion of the ion chromatogram, after suppression, on a concentrator column and reinjectin...

  8. Thin layer chromatography of diethyl dithiocarbamate complexes of inorganic ions

    Microsoft Academic Search

    J. Rai; V. P. Kukreja

    1970-01-01

    Thin Layer Chromatography separation of the cations which form extractable complexes with diethyl dithiocarbamate in acidic and basic conditions has been effected. Silver, Mercury, Copper, Lead, Palladium, Bismuth and Thallium could be separated at pHs more than 11 and Cobalt, Nickel, Chromium and Uranium at pH 6–8.

  9. Recent developments in electrolytic devices for ion chromatography

    Microsoft Academic Search

    Yan Liu; Kannan Srinivasan; Chris Pohl; Nebojsa Avdalovic

    2004-01-01

    Recent developments in new electrolytic devices that utilize the electrolysis of water and charge-selective electromigration of ions through ion-exchange media have significantly changed the routine operation of ion chromatographic methods. Examples of these new electrolytic devices include on-line eluent generators that produce high-purity electrolyte eluents using deionized water as the carrier stream, continuously regenerated trap columns that remove ionic contaminants

  10. Size Exclusion Chromatography: An Experiment for High School and Community College Chemistry and Biotechnology Laboratory Programs

    ERIC Educational Resources Information Center

    Brunauer, Linda S.; Davis, Kathryn K.

    2008-01-01

    A simple multiday laboratory exercise suitable for use in a high school or community college chemistry course or a biotechnology advanced placement biology course is described. In this experiment students gain experience in the use of column chromatography as a tool for the separation and characterization of biomolecules, thus expanding their…

  11. Fast Gas Chromatography with Short Columns: Are Speed and Resolution Mutually Exclusive?

    Microsoft Academic Search

    Nicholas H. Snow

    2005-01-01

    Recently, interest in developing techniques for very fast separations using capillary gas chromatography (GC) has increased significantly. This is probably owing to the many improvements in technology, hardware, and software over the past fifteen years. Nearly all of the fast GC instruments developed have a common characteristic, i.e., a short column. In this review, the practical implications on method development,

  12. DETERMINATION OF THE BAND BROADENING FUNCTION IN SIZE EXCLUSION CHROMATOGRAPHY WITH LIGHT-SCATTERING DETECTION

    Microsoft Academic Search

    Mariana M. Yossen; Jorge R. Vega; Taihyun Chang; Gregorio R. Meira

    2012-01-01

    This work describes the determination of the band broadening function (BBF) in a size exclusion chromatograph fitted with 2 mixed-gel columns, a light scattering (LS) detector, and a differential refractometer (DR). The raw data were the chromatograms of 4 narrow polystyrene standards. First, the interdetector volume shift was indirectly estimated from its upper and lower limiting values. Then, for each

  13. Evolution of natural organic matter by size exclusion chromatography during photocatalytic degradation by solvothermal-synthesized titanium dioxide.

    PubMed

    Valencia, Sergio H; Marín, Juan M; Restrepo, Gloria M

    2012-04-30

    This study shows the effect of different titanium dioxides in transforming the structural properties of natural organic matter (NOM) during photocatalytic degradation with a solar UV light simulator. Titanium dioxide (TiO(2)) synthesized by the sol-gel method coupled with the solvothermal technique and Degussa P-25 TiO(2) were used. The evolution of NOM degradation was followed by size exclusion chromatography with dissolved organic carbon, ultraviolet and fluorescence detection (SEC-DOC, SEC-UV(254) and SEC-Fl(254/450)). For both catalysts, there was a preferential degradation of the larger molecules of NOM into medium and smaller molecular size fractions. However, the synthesized TiO(2) was found to be more efficient than Degussa P-25 TiO(2) for DOC removal, especially UV(254) absorption and Fl(254/450) removal. PMID:22370203

  14. Molecular characterization of multivalent bioconjugates by size-exclusion chromatography (SEC) with multi-angle laser light scattering (MALS)

    PubMed Central

    Pollock, Jacob F.; Ashton, Randolph S.; Rode, Nikhil A.; Schaffer, David V.; Healy, Kevin E.

    2013-01-01

    The degree of substitution and valency of bioconjugate reaction products are often poorly judged or require multiple time- and product- consuming chemical characterization methods. These aspects become critical when analyzing and optimizing the potency of costly polyvalent bioactive conjugates. In this study, size-exclusion chromatography with multi-angle laser light scattering was paired with refractive index detection and ultraviolet spectroscopy (SEC-MALS-RI-UV) to characterize the reaction efficiency, degree of substitution, and valency of the products of conjugation of either peptides or proteins to a biopolymer scaffold, i.e., hyaluronic acid (HyA). Molecular characterization was more complete compared to estimates from a protein quantification assay, and exploitation of this method led to more accurate deduction of the molecular structures of polymer bioconjugates. Information obtained using this technique can improve macromolecular engineering design principles and better understand multivalent macromolecular interactions in biological systems. PMID:22794081

  15. Detailed characterization of hyaluronan using aqueous size exclusion chromatography with triple detection and multiangle light scattering detection.

    PubMed

    Harmon, Patricia S; Maziarz, E Peter; Liu, X Michael

    2012-10-01

    Hyaluronan (HA) has attracted great interest and attention from ophthalmic surgical and eye care companies owing to its unique properties. A more complete understanding of HA biopolymers has, therefore, become increasingly critical as thorough characterization of raw materials helps promote product quality and process control. Often, such detailed information requires the use of a combination of analytical techniques. In this study, we compared size exclusion chromatography (SEC) with online multiangle light scattering (SEC-MALS) and SEC with triple detection (SEC-TD) experiments for HA analysis. Three lots of commercially available eye drop grade HA were characterized by SEC-MALS and SEC-TD. The absolute molecular weight averages, molecular weight distribution, radius of gyration, and solution conformation of the three HA lots were determined and compared by the two techniques. In addition, the intrinsic viscosity and intrinsic viscosity distribution were measured by SEC-TD. PMID:22807073

  16. Determination of cannabinoids in cannabis products using liquid chromatography–ion trap mass spectrometry

    Microsoft Academic Search

    A. A. M. Stolker; J. van Schoonhoven; A. J. de Vries; I. Bobeldijk-Pastorova; W. H. J. Vaes; R. van den Berg

    2004-01-01

    A method was developed and validated for the simultaneous determination of five cannabinoids, viz. cannabidiol (CBD), cannabidiol acid (CBD-COOH), cannabinol (CBN), ?9-tetrahydrocannabinol (THC), and 3?-carboxy-?9-all-trans-tetrahydrocannabinol (THC-COOH) in cannabis products. The cannabinoids were extracted from the grinded cannabis samples with a mixture of methanol–chloroform and analysed using liquid chromatography with ion-trap-mass-spectrometry (LC–IT-MSn). For quantification the two most abundant diagnostic MS–MS ions

  17. Flow-injection sample preconcentration for ion-pair chromatography of trace metals in waters

    Microsoft Academic Search

    Ewa Pobo?y; Radoslav Halko; Marcin Krasowski; Tomasz Wierzbicki; Marek Trojanowicz

    2003-01-01

    Selected trace transition metal ions have been determined in an FIA\\/HPLC hyphenated system using on-line preconcentration on cellulose functionalised sorbent Cellex P. For HPLC separation ion-pair chromatography was employed with spectrophotometric detection at 510nm using post-column derivatisation with PAR. Favourable kinetic conditions of sorption and elution as well as optimisation of hyphenated system allowed to obtain detection limits at sub-?gL?1

  18. FRACTIONATION OF LITHIUM ISOTOPES IN ION EXCHANGE CHROMATOGRAPHY WITH TITANIUM PHOSPHATE EXCHANGER

    Microsoft Academic Search

    K. Ooi; Y. Miyai; Y. Makita; H. Kanoh

    1999-01-01

    Ion exchange chromatography of lithium was carried out to study the lithium isotope effect in an aqueous ion-exchange system, using titanium phosphate exchangers granulated with polyvinyl chloride or an inorganic binder. The sample granulated with PVC showed significant isotope fractionations when a 0.05 M (NH4)2CO3 solution was used as an eluent. The lighter isotope Li was preferentially fractionated into the

  19. A cation exchange resin bead-based microscale electrolytic suppressor for capillary ion chromatography

    Microsoft Academic Search

    Feifang Zhang; Yapu Li; Bingcheng Yang; Xinmiao Liang

    2011-01-01

    A cation exchange resin (CER) bead-based microscale electrolytic suppressor for capillary ion chromatography (CIC) has been fabricated and evaluated. Relative to common ion exchange membrane, the use of CER beads presents a simple way to fabricate a microscale suppressor due to its small surface area and spherical shape. The internal volume of the device is ?600nL, which matches the requirements

  20. Estimation of band broadening in size-exclusion chromatography. I. A method based on analyzing narrow standards with a molar mass-sensitive detector

    Microsoft Academic Search

    Mariana M. Yossen; Jorge R. Vega; Gregorio R. Meira

    2006-01-01

    A method is proposed for estimating the (asymmetrical and non-uniform) band broadening function (BBF) in size-exclusion chromatography (SEC). The following data are required: the molar mass calibration and the concentration- and molar mass chromatograms of a set of narrow standards. In the narrow range of each standard, the BBF is uniform but skewed. Each uniform BBF is estimated through a

  1. Analysis of commercial beverage products by size exclusion chromatography coupled with UV–vis absorbance detection and dynamic surface tension detection

    Microsoft Academic Search

    Karisa M. Pierce; Emilia Bramanti; Massimo Onor; Roberto Spiniello; Alexandra Kangas; Kristen J. Skogerboe; Robert E. Synovec

    2010-01-01

    Multidimensional analysis of instant coffee and barley beverage samples using size exclusion chromatography (SEC) combined with a dynamic surface tension detector (DSTD) and a UV–vis absorbance detector (UV) is reported. A unique finding of this study was the action of the tetrabutylammonium (TBA) cation as a modifying agent (with bromide as the counter anion) that substantially increased the surface pressure

  2. Use of ion chromatography for monitoring atmospheric pollution in background networks

    Microsoft Academic Search

    Cinzia Perrino; Maria Concetta; Tomasi Scianò; Ivo Allegrini

    1999-01-01

    The results of the application of the annular denuder–filter pack technique coupled with ion chromatography to the determination of atmospheric pollutants in semi-polluted and background areas are reported. The coupling of these techniques reveals a viable solution for the precise and accurate measurement of atmospheric pollutants, with discrimination of the gaseous and the particulate phase and without any mutual interconversion

  3. Rapid quantitative method for total brominated vegetable oil in soft drinks using ion chromatography

    Microsoft Academic Search

    Ashraf A. Yousef; Alaa B. Abbas; Bassam Sh. Badawi; Wafaa Y. Al-Jowhar; Esam A. Zain; Seham A. El-Mufti

    2012-01-01

    A simple, quantitative and rapid method for total brominated vegetable oil (BVO) using ion chromatography (IC) with suppressed conductivity detection was developed and successfully applied to soft drinks with results expressed as inorganic bromide anion. The procedure involves extraction of BVO with diethyl ether and treatment with zinc dust in a solution of acetic acid, giving recoveries ranging between 92.5

  4. Determination of residual trifluoroacetate in protein purification buffers and peptide preparations by ion chromatography

    Microsoft Academic Search

    Edward Kaiser; Jeff Rohrer

    2004-01-01

    Trifluoroacetate (TFA) is commonly used in a variety of pharmaceutical applications. Because of its toxic nature, it is important to reliably measure the effective removal of TFA. We developed an ion chromatography (IC) method to determine the concentration of residual TFA in samples found in the pharmaceutical industry. A high-capacity anion-exchange column was used to separate trace trifluoroacetate from an

  5. Analyses of Vegetable Oil Triacylglycerols by Silver Ion High Performance Liquid Chromatography with Flame Ionization Detection

    Microsoft Academic Search

    W. E. Neff; R. O. Adlof; G. R. List; M. El-Agaimy

    1994-01-01

    Silver ion high performance liquid chromatography with a commercially available column with a simple isocratic mobile phase of acetonitrile in hexane and flame ionization detection was employed to separate and quantitate triacylglycerol species of vegetable oils. Coconut, palm, cottonseed, olive, safflower, sunflower, corn, pumpkinseed, linseed, soybean, and canola oils were analyzed, as well as randomized corn and soybean oils, and

  6. Aggregation analysis of pharmaceutical human immunoglobulin preparations using size-exclusion chromatography and analytical ultracentrifugation sedimentation velocity.

    PubMed

    Krayukhina, Elena; Uchiyama, Susumu; Nojima, Kiyoko; Okada, Yoshiaki; Hamaguchi, Isao; Fukui, Kiichi

    2013-01-01

    In the pharmaceutical industry, analysis of soluble aggregates in pharmaceutical formulations is most commonly performed using size-exclusion chromatography (SEC). However, owing to concerns that aggregates can be overlooked by SEC analysis, it has been suggested that its results should be confirmed with orthogonal methods. One of the main alternative methods for SEC is analytical ultracentrifugation sedimentation velocity (AUC-SV), which has been indicated as an important tool for the measurement of protein aggregation. The present study aimed to show that AUC-SV can be effectively applied for the characterization of marketed immunoglobulin pharmaceutical preparations to support the results obtained by SEC. In addition, the present research aimed to assess the appropriateness of two integration approaches for the quantitative analysis of the SEC results. Thus, the aggregates were measured in seven different preparations of human immunoglobulins by AUC-SV and SEC, and the acquired chromatographic data were processed by using either the vertical drop method or the Gaussian skim approach, implemented in the Empower II chromatography data software (Waters, Tokyo, Japan). The results of aggregation measurements performed using AUC-SV were in good agreement with those obtained using SEC. As expected, the Gaussian skim integration approach inherently provided lower estimates of aggregation content than the results of the vertical drop method. The finding of this study confirmed the complementary nature of AUC-SV to SEC for aggregate composition analysis and underscored the important role that the different integration methods can play in the quantitative interpretation of chromatographic results. PMID:22925901

  7. Simple purification (desalting) procedure to facilitate structural analysis of an alkali-solubilized/neutralized starch solution by intermediate-pressure size-exclusion chromatography.

    PubMed

    Kim, Hyun-Seok; Huber, Kerry C

    2007-06-27

    A technique was established to remove impurities (e.g., salts) from starch dissolved in strong alkali and neutralized with acid to accommodate starch structural analysis via intermediate-pressure size-exclusion chromatography (IPSEC). Starch (corn and wheat) subjected to an alkaline-microwave dissolution scheme (35 s microwave heating in a mixture of 6 M urea and 1 M KOH) was either treated with ion-exchange resin or passed through a desalting column to remove salt/urea contaminants. Control (untreated) starch solution analyzed by IPSEC displayed a significant interfering peak (attributable to salt/urea), which coeluted with the starch amylose peak. The interfering peak was most efficiently eliminated by first passing the starch solution through a desalting column, which process effectively removed impurities (e.g., salts/urea) without appearing to adversely impact the starch structural analysis. This simple technique coupled with the rapid alkaline-microwave starch dissolution procedure greatly expedites structural investigation of starch by facilitating analysis by IPSEC. PMID:17530769

  8. On-Line Monitoring of MWD in a Batch Polymerization Reactor by Size Exclusion Chromatography

    Microsoft Academic Search

    S. Ponnuswamy; S. L. Shah; C. Kiparissides

    1986-01-01

    A novel highly automated SEC system has been developed for online measurement of MWD in a batch solution polymerization reactor. The system includes a liquid exclusion chromatograph, an automatic sampling system, a programmable microprocessor based sequence timer and a process computer. Two main real-time computer programs have been developed to supervise the automatic collection (SEC-Data Acquisition Program) and interprepation (SEC-Data

  9. Calcium isotope fractionation in ion-exchange chromatography

    Microsoft Academic Search

    W. A. Russell; D. A. Papanastassiou

    1978-01-01

    Significant fractionation of the isotopes of calcium has been observed during elution through short ion-exchange columns packed with Dowex 50W-X8 resin. A double isotopic tracer was used to provide correction for instrumental fractionation effects. The absolute ⁴°Ca\\/⁴⁴Ca ratio is determined by this method to 0.05% and provides a measure of the fractionation of all Ca isotopes. It is found that

  10. Reverse-phase ion-pair chromatography (HPLC) (high performance liquid chromatography) of alkylbenzene sulfonates

    SciTech Connect

    Verkruyse, L.A.; Lewis, R.V.; Meyers, K.O.; Salter, S.J.

    1983-01-01

    An HPLC procedure is presented that rapidly and quantitatively separates alkylbenzene sulfonates according to their alkyl chain length and structure. The separation employs octadecylsilanized silica gel as a stationary phase and an aqueous acetonitrile solution of tetrabutyl ammonium chloride (TBAC) as the mobile phase. The TBAC acts as an ion-pair reagent and suppresses the ionic nature of the sulfonates. Separation is effected by gradients in TBAC concentration and mobile phase polarity. The concentration of each component then is quantitatively measured by a UV detector. Gradient selection and sample matrix effects are discussed. Several examples are presented that demonstrate the utility of this analytic procedure. 14 references.

  11. Simultaneous speciation of iron(II) and iron(III) by ion chromatography with chemiluminescence detection.

    PubMed

    Chen, Yun-Chieh; Jian, Yu-Ling; Chiu, Kong-Hwa; Yak, Hwa-Kwang

    2012-01-01

    This study reports on a method for the speciation of iron in aqueous samples by the simultaneous analysis of divalent and trivalent iron ions with ion chromatography equipped with chemiluminescence detection (IC-CLD). Ferrous and ferric ions are first chelated by pyridine-2,6-dicarboxylic acid (PDCA) to form complexed anions, and separated by a mixed-bed ion-exchange column. The separated complexed ions are then detected with a CLD system containing luminol and hydrogen peroxide in a basic solution. This luminescence system has a linear dynamic range of ca. 3 orders of magnitude, with method detection limits as low as 7 µg L(-1) for Fe(II) and 3 µg L(-1) for Fe(III), measured in the simultaneous detection mode. This system resists interferences from common cations such as Cd, Ca, Cr, Cu, Mg, Ni, Pb, and Zn. Evaluation by analyzing real samples shows that this method is rapid, accurate, sensitive, and selective. PMID:22878635

  12. Determination of flavone, flavonol, and flavanone aglycones by negative ion liquid chromatography electrospray ion trap mass spectrometry

    Microsoft Academic Search

    Nicolas Fabre; Isabelle Rustan; Edmond de Hoffmann; Joëlle Quetin-Leclercq

    2001-01-01

    Eleven naturally occurring flavonoid aglycones, belonging to the representative flavone, flavonol, and flavanone types were\\u000a separated by high performance liquid chromatography and analyzed on-line with negative ion electrospray ionization tandem\\u000a mass spectrometry (ESI-MS\\/MS). In order to resolve the MS\\/MS spectra obtained, each compound was reinvestigated by direct\\u000a loop injections using an ion trap mass spectrometer. The MS\\u000a n\\u000a spectra obtained

  13. Quantifying accumulation or exclusion of H+, HO?, and Hofmeister salt ions near interfaces

    PubMed Central

    Pegram, L. M.; Record, M. T.

    Recently, surface spectroscopies and simulations have begun to characterize the non-uniform distributions of salt ions near macroscopic and molecular surfaces. The thermodynamic consequences of these non-uniform distributions determine the often-large ion-specific effects of Hofmeister salts on a very wide range of processes in water. For uncharged surfaces, where these nonuniform ion distributions are confined to the first few layers of water at the surface, a two-state approximation to the distributions of water and ions, called the salt ion partitioning model (SPM) has both molecular and thermodynamic signiicance. Here, we summarize SPM results quantifying the local accumulation of H+, exclusion of HO?, and range of partitioning behavior of Hofmeister anions and cations near macroscopic and molecular interfaces. These results provide a database to interpret or predict Hofmeister salt effects on aqueous processes in terms of structural information regarding amount and composition of the surface exposed or buried in these processes. PMID:23750042

  14. Fabricating electrospun cellulose nanofibre adsorbents for ion-exchange chromatography.

    PubMed

    Dods, Stewart R; Hardick, Oliver; Stevens, Bob; Bracewell, Daniel G

    2015-01-01

    Protein separation is an integral step in biopharmaceutical manufacture with diffusion-limited packed bed chromatography remaining the default choice for industry. Rapid bind-elute separation using convective mass transfer media offers advantages in productivity by operating at high flowrates. Electrospun nanofibre adsorbents are a non-woven fibre matrix of high surface area and porosity previously investigated as a bioseparation medium. The effects of compression and bed layers, and subsequent heat treatment after electrospinning cellulose acetate nanofibres were investigated using diethylaminoethyl (DEAE) or carboxylate (COO) functionalisations. Transbed pressures were measured and compared by compression load, COO adsorbents were 30%, 70% and 90% higher than DEAE for compressions 1, 5 and 10MPa, respectively, which was attributed to the swelling effect of hydrophilic COO groups. Dynamic binding capacities (DBCs) at 10% breakthrough were measured between 2000 and 12,000CV/h (2s and 0.3s residence times) under normal binding conditions, and DBCs increased with reactant concentration from 4 to 12mgBSA/mL for DEAE and from 10 to 21mglysozyme/mL for COO adsorbents. Comparing capacities of compression loads applied after electrospinning showed that the lowest load tested, 1MPa, yielded the highest DBCs for DEAE and COO adsorbents at 20mgBSA/mL and 27mglysozyme/mL, respectively. At 1MPa, DBCs were the highest for the lowest flowrate tested but stabilised for flowrates above 2000CV/h. For compression loads of 5MPa and 10MPa, adsorbents recorded lower DBCs than 1MPa as a result of nanofibre packing and reduced surface area. Increasing the number of bed layers from 4 to 12 showed decreasing DBCs for both adsorbents. Tensile strengths were recorded to indicate the mechanical robustness of the adsorbent and be related to packing the nanofibre adsorbents in large scale configurations such as pleated cartridges. Compared with an uncompressed adsorbent, compressions of 1, 5 and 10MPa showed increases of 30%, 110% and 110%, respectively, for both functionalisations. The data presented show that capacity and mechanical strength can be balanced through compression after electrospinning and is particular to different functionalisations. This trade-off is critical to the development of nanofibre adsorbents into different packing configurations for application and scale up in bioseparation. PMID:25541092

  15. Simultaneous determination of trace oxyhalides and haloacetic acids using suppressed ion chromatography-electrospray mass spectrometry

    Microsoft Academic Search

    Leon Barron; Brett Paull

    2006-01-01

    A new analytical procedure for the simultaneous determination of trace oxyhalides and haloacetic acids (HAs) in drinking water and aqueous soil extracts is described. The method uses micro-bore ion chromatography (IC) coupled with suppressed conductivity (SC) and electrospray ionization mass spectrometric detection (ESI-MS). The IC–SC–ESI-MS system included a secondary flow of 100% MeOH, which was added to the column eluate

  16. Analysis of oxyhalides in water by ion chromatography–ionspray mass spectrometry

    Microsoft Academic Search

    L Charles; D Pépin

    1998-01-01

    A sensitive method for analyzing chlorite, chlorate, bromate and iodate in water by ion chromatography (IC) coupled with ionspray tandem mass spectrometry (IS-MS–MS) has been developed. Prior to analysis, samples were subjected to off-line sample clean-up with Ba, Ag and H-form resins to remove sulfate, chloride and hydrogencarbonate, respectively. Oxyhalides in the purified samples were concentrated and separated on a

  17. Determination of copper and zinc in blood plasma by ion chromatography using a cobalt internal standard

    Microsoft Academic Search

    Alexis J. Holden; Robert A. Cowardb

    1999-01-01

    Ion chromatography was used to detect levels of copper and zinc in blood plasma from renal dialysis patients on continuous ambulatory peritoneal dialysis (CAPD) and haemodialysis (HD). The developed method used cobalt as an internal standard and when combined with the standard additions method improved the overall precision of the results by between 20.3 and 6.0% and 20.8 and 5.7%

  18. Liquid chromatography with electrospray ion-trap mass spectrometry for the determination of yessotoxins in shellfish

    Microsoft Academic Search

    M Fernández Amandi; A Furey; M Lehane; H Ramstad; K. J James

    2002-01-01

    Yessotoxins are a group of large polyether toxins, produced by marine dinoflagellates, which cause widespread contamination of filter-feeding shellfish. A new, sensitive liquid chromatography–mass spectrometry (LC–MS) method has been developed for the determination of yessotoxin (YTX) and 45-hydroxy-yessotoxin (45-OHYTX), a major metabolite in shellfish. The LC system was coupled, via an electrospray ionisation (ESI) source, to an ion-trap MS in

  19. Purification of C-Phycocyanin from Spirulina platensis by Single-Step Ion-Exchange Chromatography

    Microsoft Academic Search

    Xiaoxia Liao; Bochao Zhang; Xiaoqin Wang; Huidan Yan; Xuewu Zhang

    2011-01-01

    C-Phycocyanin is a natural blue pigment with many commercial applications in foods, cosmetics, and medicines. In this paper\\u000a we describe the extraction and purification of C-phycocyanin from the cyanobacterium Spirulina platensis. The procedure is based on adsorption of impurities with chitosan and activated charcoal then one-step ion-exchange chromatography.\\u000a The dry algal powder was soaked in potassium phosphate buffer for 2 h

  20. Nitric oxide in biological fluids: analysis of nitrite and nitrate by high-performance ion chromatography

    Microsoft Academic Search

    Steven A. Everett; Madeleine F. Dennis; Gillian M. Tozer; Vivien E. Prise; Peter Wardman; Michael R. L. Stratford

    1995-01-01

    The analysis of nitric oxide-derived nitrite and nitrate ions in biological fluids represents a proven strategy for determining nitric oxide participation in a diverse range of physiological and pathophysiological processes in vivo. In this article we describe a versatile method for the simultaneous measurement of NO2? and NO3? anions in both plasma and isolated tumour models based on anion-exchange chromatography

  1. Differentiation of the halogen content of peat samples using ion chromatography after combustion (TX\\/TOXIC)

    Microsoft Academic Search

    Anke Putschew; Frank Keppler; Martin Jekel

    2003-01-01

    The proposed method for the differential AOX analysis of water samples was tested for its applicability to differentiate the halogen content of peat samples. For determination of the total and the total organic-bound chlorine, bromine and iodine, peat samples were combusted, and the combustion gases trapped and analyzed by ion chromatography (TX\\/TOX-IC). The total and the organically bound chlorine, bromine

  2. Ultraperformance liquid chromatography with electrospray ionization ion trap mass spectrometry for chondroitin disaccharide analysis

    Microsoft Academic Search

    Kemal Solakyildirim; Zhenqing Zhang; Robert J. Linhardt

    2010-01-01

    Chondroitin sulfate (CS) has an important role in cell division, in the central nervous system, and in joint-related pathologies such as osteoarthritis. Due to the complex chemical structure and biological importance of CS, simple, sensitive, high resolution, and robust analytical methods are needed for the analysis of CS disaccharides and oligosaccharides. An ion-pairing, reversed-phase, ultraperformance liquid chromatography (IPRP–UPLC) separation, coupled

  3. Electrophoresis and size-exclusion chromatography of humic substances extracted from detritus and soils of different geneses

    NASA Astrophysics Data System (ADS)

    Trubetskaya, O. E.; Trubetskoi, O. A.; Borisov, B. A.; Ganzhara, N. F.

    2008-02-01

    Electrophoresis in 10% polyacrylamide gel in the presence of denaturants and size-exclusion chromatography in Sephadex G-75 in 7 M urea were used for the comparative analysis of humic substances isolated from a typical chernozem, soddy-podzolic soil, and chestnut soil and from the easily decomposable organic matter (plant detritus) contained in these soils. After the electrophoresis, the gel with naturally colored bands of humic substances was further stained with a dye specific for proteins by immersing into a solution containing Coomassie Brilliant Blue R-250 and CuSO4. The electrophoretic and chromatographic analyses showed that humic substances from the soils and the corresponding detritus fractions significantly differed in the intensity of the natural color of the electrophoretic fractions, the molecular-weight distribution, and the color of the electrophoretic fractions colored by the protein-specific dye (which was first discovered in this study). The hypothesis of Tyurin and Aleksandrova suggesting that the transformation of humus sources (plant detritus) into humic substances proceeds in the direction from the high-molecular compounds to the low-molecular compounds was experimentally confirmed.

  4. Estimation of the band broadening parameters in single detection size-exclusion chromatography: a comparative study of various column combinations.

    PubMed

    Schnöll-Bitai, Irene; Vega, Jorge; Mader, Christoph

    2007-11-26

    Alternative approaches for the determination of band broadening in size-exclusion chromatography based on the use of exponentially modified Gaussian (EMG) functions were used to experimentally investigate the performance of two different column sets. In both cases, the columns were combined in order to cover the complete fractionation range (from 10(3) to 5x10(6) g mol(-1)), which is of interest in many applications. When analyzing experimental chromatograms the question of proper data treatment (especially the necessary smoothing routines) became obvious and is discussed accordingly. First results indicate that the exponential decay time of the EMG decreases and the standard deviation of its Gaussian component slightly increases (or remains almost constant) with increasing retention volumes. As a consequence, the total variance and the asymmetry of the EMG both decrease with the retention volume. A favorable agreement with independent experimental results (obtained by other researchers on the basis of analyzing ultra narrow standards) was found. Additionally, the skew was also investigated as a function of the retention volume and the trend was found to be in concordance with the predictions of theoretical models. The comparison with theoretical models is also discussed. PMID:17983775

  5. Alternative approaches for the estimation of the band broadening parameters in single-detection size exclusion chromatography.

    PubMed

    Vega, Jorge R; Schnöll-Bitai, Irene

    2005-11-18

    New approaches for the determination of the extent of symmetric and asymmetric band broadening (BB) in size exclusion chromatography (SEC) are presented. For this purpose raw data was simulated by starting with either a theoretical Poisson number chain length distribution (NCLD), or a log-normal weight chain length distribution (WCLD). Each distribution was first converted to a BB-free mass chromatogram, as typically obtained from a standard differential refractive index detector. Then, the broadened (or "measured") chromatograms were simulated by convoluting the BB-free chromatograms with a BB function, which was assumed to follow symmetrical (Gauss) as well as unsymmetrical (exponentially modified Gauss) function. A broad range of BB parameters (standard deviation, sigma(BB), and exponential decay, tau(BB)) was used for the simulations. The approaches are based on the determination of the points of inflection belonging to the peak of the broadened chromatogram, and closed as well as empirically derived equations connecting the peak width, its variance, and the parameters sigma(BB) and tau(BB). The developed methods are applicable for Poisson distributions well above a peak chain length of 100. PMID:16275289

  6. High-pressure size exclusion chromatography analysis of dissolved organic matter isolated by tangential-flow ultra filtration

    USGS Publications Warehouse

    Everett, C.R.; Chin, Y.-P.; Aiken, G.R.

    1999-01-01

    A 1,000-Dalton tangential-flow ultrafiltration (TFUF) membrane was used to isolate dissolved organic matter (DOM) from several freshwater environments. The TFUF unit used in this study was able to completely retain a polystyrene sulfonate 1,800-Dalton standard. Unaltered and TFUF-fractionated DOM molecular weights were assayed by high-pressure size exclusion chromatography (HPSEC). The weight-averaged molecular weights of the retentates were larger than those of the raw water samples, whereas the filtrates were all significantly smaller and approximately the same size or smaller than the manufacturer-specified pore size of the membrane. Moreover, at 280 nm the molar absorptivity of the DOM retained by the ultrafilter is significantly larger than the material in the filtrate. This observation suggests that most of the chromophoric components are associated with the higher molecular weight fraction of the DOM pool. Multivalent metals in the aqueous matrix also affected the molecular weights of the DOM molecules. Typically, proton-exchanged DOM retentates were smaller than untreated samples. This TFUF system appears to be an effective means of isolating aquatic DOM by size, but the ultimate size of the retentates may be affected by the presence of metals and by configurational properties unique to the DOM phase.

  7. Evaluation of size exclusion chromatography (SEC) for the characterization of extracellular polymeric substances (EPS) in anaerobic granular sludges.

    PubMed

    Simon, Stéphane; Païro, Bérengère; Villain, Maud; D'Abzac, Paul; Van Hullebusch, Eric; Lens, Piet; Guibaud, Gilles

    2009-12-01

    The extracellular polymeric substances (EPS) extracted from three granular and one flocculant anaerobic sludges were characterised by size exclusion chromatography (SEC) using two serially linked chromatographic columns in order to obtain more detailed chromatograms. A Superdex peptide 10/300 GL (0.1-7 kDa) and Superdex 20010/300 GL (10-600 kDa) from Amersham Biosciences were used in series with a mobile phase at pH 7 with an ionic strength of 0.223 M (phosphate buffer 50 mM and NaCl 150 mM). A part of the EPS molecules displays hydrophobic and/or ionic interactions with the column packing. Interactions could be modified by changing the mobile phase ionic strength or polarity (addition of acetonitrile). The detection wavelength (210 or 280 nm) affects strongly the EPS chromatogram. For a sludge originating from the same type of biofilms (i.e., anaerobic granules), the differences in EPS fingerprints are mainly due to differences in the absorbance of the chromatographic peaks, linked to EPS molecules content and composition. The EPS fingerprint changes significantly when the EPS originate from another type of anaerobic sludges. In addition, EPS fingerprints were affected by the extraction method used (centrifugation only; heat and centrifugation or cationic exchange resin and centrifugation). This phenomenon was observed mainly for the largest and smallest molecules and molecules which display interactions with column packing. PMID:19660939

  8. Branched-polymer separations using comprehensive two-dimensional molecular-topology fractionation x size-exclusion chromatography.

    PubMed

    Edam, R; Meunier, D M; Mes, E P C; Van Damme, F A; Schoenmakers, P J

    2008-08-01

    Branching has a strong influence on the processability and properties of polymers. However, the accurate characterization of branched polymers is genuinely difficult. Branched molecules of a certain molecular weight exhibit the same hydrodynamic volumes as linear molecules of substantially lower weights. Therefore, separation by size-exclusion chromatography (SEC), will result in the co-elution of molecules with different molecular weights and branching characteristics. Chromatographic separation of the polymer molecules in sub-microm channels, known as molecular-topology fractionation (MTF), may provide a better separation based on topological differences among sample molecules. MTF elution volumes depend on both the topology and molar mass. Therefore co-elution of branched molecules with linear molecules of lower molar mass may also occur in this separation. Because SEC and MTF exhibit significantly different selectivity, the best and clearest separations can be achieved by combining the two techniques in a comprehensive two-dimensional (MTFxSEC) separation system. In this work such a system has been used to demonstrate branching-selective separations of star branched polymers and of randomly long-chain-branched polymers. Star-shaped polymers were separated from linear polymers above a column-dependent molecular weight or size. PMID:18550074

  9. Online high-performance size exclusion chromatography-nuclear magnetic resonance for the characterization of dissolved organic matter.

    PubMed

    Woods, Gwen C; Simpson, Myrna J; Kelleher, Brian P; McCaul, Margaret; Kingery, William L; Simpson, André J

    2010-01-15

    The substantial heterogeneity of dissolved organic matter (DOM) inhibits detailed chromatographic analysis with conventional detectors as little structural information can be obtained in the presence of extensive coelution. Here we examine the direct hyphenation of high-performance size exclusion chromatography (HPSEC) with nuclear magnetic resonance (NMR) spectroscopy to determine how size-distinguished fractions differ in composition. The results support the applicability of using HPSEC to generate more homogeneous fractions of DOM prior to NMR analysis and demonstrate that structure is significantly altered with size. The largest fractions are enriched in carbohydrate- and aromatic-type structures. The midsized material is substantial and is representative of carboxyl-rich alicyclic molecules (CRAMs). The smallest material has strong signatures of material derived from linear terpenoids (MDLT). Both CRAMs and MDLT have been recently hypothesized as major components of DOM, and detection by HPSEC-NMR confirms their existence as unique and separable entities. This preliminary work focuses on NMR hyphenation to HPSEC due to widespread use of HPSEC to characterize DOM. Online hyphenation is useful not only for time-efficient analysis of DOM but also for that of other highly complex samples such as those found in many environmental analyses. PMID:20030309

  10. Comparison of liquid chromatography using triple quadrupole and quadrupole ion trap mass analyzers to determine pesticide residues in oranges

    Microsoft Academic Search

    Carla Soler; Jordi Mañes; Yolanda Picó

    2005-01-01

    Liquid chromatography-triple quadrupole\\/mass spectrometry (LC-TQ\\/MS) and liquid chromatography-quadrupole ion trap\\/mass spectrometry (LC-QIT\\/MS) for determining bupirimate, hexaflumuron, tebufenpyrad, buprofezin, pyriproxyfen, and fluvalinate in fruits have been compared. The differences in the mass spectra obtained by triple and ion trap quadrupoles are discussed, showing how both of them provide interesting features. The evaluation of the two instruments was carried out by ethyl

  11. Determination of alkylamines in atmospheric aerosol particles: a comparison of gas chromatography-mass spectrometry and ion chromatography approaches

    NASA Astrophysics Data System (ADS)

    Huang, R.-J.; Li, W.-B.; Wang, Y.-R.; Wang, Q. Y.; Jia, W. T.; Ho, K.-F.; Cao, J. J.; Wang, G. H.; Chen, X.; Haddad, I. EI; Zhuang, Z. X.; Wang, X. R.; Prévôt, A. S. H.; O'Dowd, C. D.; Hoffmann, T.

    2014-07-01

    In recent years low molecular weight alkylamines have been recognized to play an important role in particle formation and growth in the lower atmosphere. However, major uncertainties are associated with their atmospheric processes, sources and sinks, mostly due to the lack of ambient measurements and the difficulties in accurate quantification of alkylamines at trace level. In this study, we present the evaluation and optimization of two analytical approaches, i.e., gas chromatography-mass spectrometry (GC-MS) and ion chromatography (IC), for the determination of alkylamines in aerosol particles. Alkylamines were converted to carbamates through derivatization with isobutyl chloroformate for GC-MS determination. A set of parameters affecting the analytical performances of the GC-MS approach, including reagent amount, reaction time and pH value, was evaluated and optimized. The accuracy is 84.3-99.1%, and the limits of detection obtained are 1.8-3.9 pg (or 0.02-0.04 ng m-3). For the IC approach, a solid-phase extraction (SPE) column was used to separate alkylamines from interfering cations before IC analysis. 1-2% (v/v) of acetone (or 2-4% (v/v) of acetonitrile) was added to the eluent to improve the separation of alkylamines on the IC column. The limits of detection obtained are 2.1-15.9 ng (or 0.9-6.4 ng m-3), and the accuracy is 55.1-103.4%. The lower accuracy can be attributed to evaporation losses of amines during the sample concentration procedure. Measurements of ambient aerosol particle samples collected in Hong Kong show that the GC-MS approach is superior to the IC approach for the quantification of primary and secondary alkylamines due to its lower detection limits and higher accuracy.

  12. Size-Exclusion Chromatography with On-Line Light-Scattering, Absorbance, and Refractive Index Detectors for Studying Proteins and Their Interactions

    Microsoft Academic Search

    Jie Wen; Tsutomu Arakawa; John S. Philo

    1996-01-01

    Techniques of using size-exclusion chromatography (SEC) with on-line light-scattering, uv absorbance, and refractive index detectors to characterize the polypeptide molecular weights of simple proteins or glycoproteins or to determine the stoichiometry of protein complexes are described. Two unique advantages of this approach over conventional SEC are that the molecular weight measurement is independent of elution position and can exclude the

  13. Molecular weight determination of hypromellose acetate succinate (HPMCAS) using size exclusion chromatography with a multi-angle laser light scattering detector.

    PubMed

    Fukasawa, Miyuki; Obara, Sakaé

    2004-11-01

    The molecular weight of hypromellose acetate succinate (HPMCAS), a polymer used for enteric coating, was determined by means of size exclusion chromatography with a multi-angle laser light scattering detector. The weight-average molecular weight (Mw) of several lots and grades ranged approximately from 17000 to 20000, and the number-average molecular weight (Mn) was around 13000. The inter-day precision of measurement, in terms of the coefficient of variation, was less than 5%. PMID:15516773

  14. Fractionation of polyethylene glycol particles by simulated moving bed with size-exclusion chromatography.

    PubMed

    Liang, Ming-Tsai; Liang, Ru-Chien

    2012-03-16

    In this study, a three-section simulated moving bed (SMB) with an open-loop design is used to fractionate polyethylene glycol (PEG) with different molecular weights. The purchased PEGs are mixed and separated by the open-loop SMB. A size-exclusion column with a pore size ranging from 10 to 100 nm, TOSOH GMPW 7.5 mm × 30 cm, is used to separate the mixtures. Based on the Triangle theory, the operating parameters of the SMB are determined and used to separate the three binary mixtures. The results show that the PEG mixtures with molecular weights of 400 and 8000, and those of 1500 and 20,000, are separable, yet those of 1500 and 3500 are difficult to separate by the selected column. The relative elution for molecular weights of 400 and 8000, and 1500 and 2000, is 1.49 and 1.54, respectively, resulting in easy separation. However, the difference in the elution volume for mixtures with molecular weights of 1500 and 3500 is so small that the operation condition is confined to a tiny area on the (m(2), m(3)) plane defined by the Triangle theory. This makes robust application of the SMB impossible. Fortunately, it is still possible to obtain pure raffinate with low recovery, but a pure extract is still not possible. It is concluded that the low selectivity of the binary mixture and the fluctuation of the operation result in the difficulty in separating the 1500 and 3000 molecular weight mixtures. This paper presents the operation procedures, including the selection of the column, the discovery of selectivity, the application of the Triangle theory and the experimental results, in order to illustrate how to apply an SMB to the fractionation of PEGs. PMID:22293284

  15. Specific screening method for dextran and hydroxyethyl starch in human urine by size exclusion chromatography-in-source collision-induced dissociation-time-of-flight mass spectrometry.

    PubMed

    Kolmonen, Marjo; Leinonen, Antti; Kuuranne, Tiia; Pelander, Anna; Deventer, Koen; Ojanperä, Ilkka

    2011-08-01

    The use of plasma volume expanders (PVE), such as dextran (DEX) and hydroxyethyl starch (HES), is prohibited in sports. DEX is a naturally occurring glucose polymer, whereas HES is synthetically produced from amylopectin starch by substitution with hydroxyethyl groups. In doping control, the commonly applied enzymatic and colorimetric screening methods are lacking adequate specificity for DEX and HES. Also, gas chromatographic-mass spectrometic (GC-MS) screening methods have specificity issues with DEX. In addition, due to the nature of the target compounds, time-consuming derivatisation steps are required in GC-MS. Based on the high molecular weight of carbohydrate polymers excreted in urine after administration of DEX and HES, a screening method was developed involving size exclusion chromatography (SEC) combined with time-of-flight mass spectrometry (TOFMS). By using solely a SEC guard column as an analytical column allowed sufficient chromatographic resolution in a minimal amount of time and with reasonable repeatability (average RSD of 10%). Detector response was linear throughout the measurement range with R(2)?>?0.99 for both analytes. Limits of detection were 100 and 250 ?g mL(-1) for DEX and HES, respectively. Ion suppression was found to be 52% at maximum. In-source collision-induced dissociation (ISCID) was used to produce characteristic fragments at a mass accuracy better than 2 mDa. The specificity of the SEC-ISCID-TOFMS method was demonstrated with 120 PVE negative doping control samples analyzed in parallel with a routine GC-MS screening method. In addition, seven urine samples from diabetic athletes, causing interpretation problems in routine GC-MS, showed here a definitely negative profile. PMID:21416163

  16. Determination of fungicide residues in baby food by liquid chromatography-ion trap tandem mass spectrometry.

    PubMed

    Gilbert-López, Bienvenida; García-Reyes, Juan F; Molina-Díaz, Antonio

    2012-11-15

    Current European Commission Directives on foods for infants and young children places emphasis on the control of pesticide residues at levels below 10 ?g kg(-1). In the present work, a liquid chromatography electrospray ionisation ion trap tandem mass spectrometry (LC-Ion Trap-MS/MS) has been developed for the multiresidue of 10 multiclass fungicides (carbendazim, thiabendazole, imazalil, tridemorph, triadimefon, bitertanol, prochloraz, flutriafol, myclobutanil and diphenylamine) in fruit-based baby food. The developed method is based on a simple sample treatment (QuEChERS), which consists of a liquid-liquid extraction using acetonitrile, followed by a clean-up step based on dispersive solid-phase extraction with primary secondary amine (PSA). Subsequent identification and quantitation was accomplished by liquid chromatography/electrospray tandem mass spectrometry using an ion-trap mass spectrometer in the product ion scan MS/MS mode. Matrix effects were evaluated in LC-MS and LC-MS/MS mode experiments, obtaining a reduction of these effects when working in MS/MS mode for most of the analytes. Limits of detection (LOD) were between 0.5 and 3.0 ?g kg(-1) depending on the pesticide studied, all being within European Union regulations for baby food. Finally, the proposed method was applied to 25 baby food samples obtained from local supermarkets. Imazalil, thiabendazole and carbendazim were detected in the studied samples. However, none of the samples tested were found to be upper the EU standard. PMID:22868159

  17. High-capacity cation-exchange column for enhanced resolution of adjacent peaks of cations in ion chromatography.

    PubMed

    Rey, M A

    2001-06-22

    One of the advantages of ion chromatography [Anal Chem. 47 (1975) 1801] as compared to other analytical techniques is that several ions may be analyzed simultaneously. One of the most important contributions of cation-exchange chromatography is its sensitivity to ammonium ion, which is difficult to analyze by other techniques [J. Weiss, in: E.L. Johnson (Ed.), Handbook of Ion Chromatography, Dionex, Sunnyvale, CA, USA]. The determination of low concentrations of ammonium ion in the presence of high concentrations of sodium poses a challenge in cation-exchange chromatography [J. Weiss, Ion Chromatography, VCH, 2nd Edition, Weinheim, 1995], as both cations have similar selectivities for the common stationary phases containing either sulfonate or carboxylate functional groups. The task was to develop a new cation-exchange stationary phase (for diverse concentration ratios of adjacent peaks) to overcome limitations experienced in previous trails. Various cation-exchange capacities and column body formats were investigated to optimize this application and others. The advantages and disadvantages of two carboxylic acid columns of different cation-exchange capacities and different column formats will be discussed. PMID:11453025

  18. Determination of trace level bromate and perchlorate in drinking water by ion chromatography with an evaporative preconcentration technique

    Microsoft Academic Search

    Yongjian Liu; Shifen Mou; Shawn Heberling

    2002-01-01

    A simple sample preconcentration technique employing microwave-based evaporation for the determination of trace level bromate and perchlorate in drinking water with ion chromatography is presented. With a hydrophilic anion-exchange column and a sodium hydroxide eluent in linear gradient, bromate and perchlorate can be determined in one injection within 35 min. Prior to ion chromatographic analysis, the drinking water sample was

  19. Ion Exchange Chromatography and Mass Spectrometric Methods for Analysis of Cadmium-Phytochelatin (II) Complexes

    PubMed Central

    Merlos Rodrigo, Miguel Angel; Cernei, Natalia; Kominkova, Marketa; Zitka, Ondrej; Beklova, Miroslava; Zehnalek, Josef; Kizek, Rene; Adam, Vojtech

    2013-01-01

    In this study, in vitro formed Cd-phytochelatin (PC2) complexes were characterized using ion exchange chromatography (IEC) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. The ratio of both studied compounds as well as experimental conditions were optimized. The highest yield of the complex was observed under an applied concentration of 100 µg·mL?1 PC2 and 100 µg·mL?1 of CdCl2. The data obtained show that IEC in combination with MALDI-TOF is a reliable and fast method for the determination of these complexes. PMID:23538727

  20. Determination of adenosine nucleotides in cultured cells by ion-pairing liquid chromatography–electrospray ionization mass spectrometry

    Microsoft Academic Search

    Tianxiu Qian; Zongwei Cai; M. S Yang

    2004-01-01

    A method using ion-pairing liquid chromatography–mass spectrometry (MS) was developed for analyzing adenosine 5?-monophosphate (AMP), adenosine 5?-diphosphate (ADP), and adenosine 5?-triphosphate (ATP) in cellular extracts. Dimethylhexylamine (DMHA) was used as ion-pairing agent to retain and separate the analytes on a reversed-phase microbore column with a gradient program. Positive-ion electrospray ionization–MS was applied for the detection because of the use of

  1. Studies of signal suppression in liquid chromatography–electrospray ionization mass spectrometry using volatile ion-pairing reagents

    Microsoft Academic Search

    Sven Åke Gustavsson; Jenny Samskog; Karin E. Markides; Bengt Långström

    2001-01-01

    Volatile ion-pairing reagents are useful due to their compatibility with liquid chromatography–electrospray ionization (ESI) mass spectrometry. In this study trifluoroacetic acid, heptafluorobutanoic acid and perfluoroheptanoic acid were used as ion-pairing reagents. The signal intensities of eight amine analytes were measured in the presence of these fluorinated carboxylic acids and compared with the signal intensity when using an ion-pair free formic

  2. A new type of metal chelate affinity chromatography using trivalent lanthanide ions for phosphopeptide enrichment.

    PubMed

    Mirza, Munazza R; Rainer, Matthias; Messner, Christoph B; Güzel, Yüksel; Schemeth, Dieter; Stasyk, Taras; Choudhary, Muhammad I; Huber, Lukas A; Rode, Bernd M; Bonn, Günther K

    2013-05-21

    In this study, a new type of immobilized metal-ion affinity chromatography (IMAC) resin for the isolation of phosphopeptides was synthesized which is based on the specific interaction between phosphate groups and chelated lanthanide metal ions. In this regard trivalent lanthanum, holmium and erbium ions were chelated to a highly porous phosphonate polymer which was prepared by radical polymerization of vinylphosphonic acid (VPA) and divinylbenzene (DVB). The developed method was evaluated with peptide mixtures from digested standard proteins (?-casein, ?-casein and ovalbumin) as well as with bovine milk, egg white and a spiked HeLa cell lysate. Compared to the commonly used TiO2 approach, the presented method showed higher selectivity for phosphorylated peptides. This can be explained by the strong preference of trivalent lanthanide ions for phosphates with which they form very tight ionic bonds. Mono- and multiply phosphorylated peptides could be enriched and released in a single basic elution step, while non-phosphorylated peptides remained on the resin. Ab initio quantum mechanical energy minimizations of model complexes for polymer-ion-ligand interactions provided geometries, binding energies and charges which are discussed in conjunction with the observed experimental properties, leading to the most satisfying agreement. The presented lanthanide-IMAC resins represent promising affinity materials for the selective isolation of phosphopeptides from biological samples. PMID:23552617

  3. [Simultaneous determination of ammonium and six alkylamines in cosmetics by ion chromatography].

    PubMed

    Zhong, Zhixiong; Li, Gongke; Zhu, Binghui; Luo, Zhibin; Wu, Ximei

    2010-07-01

    A method for the simultaneous determination of ammonium and six alkylamines in cosmetic products by ion chromatography (IC) was developed. The sample pretreatment process and the separation resolution of chromatography were investigated. The samples were extracted by 100 mmol/L acetic acid-20% (v/v) acetonitrile solution at room temperature, and then solid phase extraction (SPE) column was used to eliminate the interferences. The influences of pH value, organic solvent and coexisted ions were investigated. The separation was carried out on IonPac CS17 (250 mm x 4 mm)analytical column and IonPac CG17 (50 mm x 4 mm)guard column using 1.5 - 15 mmol/L methanesulfonic acid and 0.5% - 5% (v/v) acetonitrile gradient elution at a flow rate of 1.0 mL/min at 24 degrees C, coupled with suppressed conductivity detector. Under the optimum conditions, a measurement could be completed less than 26 min. The linearity ranged from 0.3 to 15 mg/L, the detection limits and the quantification limits were in the ranges of 2.1 - 7.9 mg/kg and 7 - 26 mg/kg, respectively. The method was successfully employed for the determination of ammonium, methylamine, dimethylamine, trimethylamine, ethylamine, propylamine and butylamine in samples including cleaning, body lotion, skin-bleaching, sun block, marcel, hair dye and pilatory cosmetics with the recoveries of 80.2% - 109.2% and the relative standard deviations (RSDs) of 0.5% - 3.1%. The method offered high selectivity, sensitivity, and gave satisfactory results for real sample analysis. PMID:21046791

  4. Determination of perchlorate in infant formula by isotope dilution ion chromatography/tandem mass spectrometry

    PubMed Central

    Wang, Z.; Lau, B.P.-Y.; Tague, B.; Sparling, M.; Forsyth, D.

    2011-01-01

    A sensitive and selective isotope dilution ion chromatography/tandem mass spectrometry (ID IC-MS/MS) method was developed and validated for the determination of perchlorate in infant formula. The perchlorate was extracted from infant formula by using 20 ml of methanol and 5 ml of 1% acetic acid. All samples were spiked with 18O4 isotope-labelled perchlorate internal standard prior to extraction. After purification on a graphitised carbon solid-phase extraction column, the extracts were injected into an ion chromatography system equipped with an Ionpac AS20 column for separation of perchlorate from other anions. The presence of perchlorate in samples was quantified by isotope dilution mass spectrometry. Analysis of both perchlorate and its isotope-labelled internal standard was carried out on a Waters Quattro Ultima triple quadrupole mass spectrometer operating in a multiple reaction monitoring (MRM) negative ionisation mode. The method was validated for linearity and range, accuracy, precision, sensitivity, and matrix effects. The limit of quantification (LOQ) was 0.4 ?g 1?1 for liquid infant formula and 0.95 ?g kg?1 for powdered infant formula. The recovery ranged from 94% to 110% with an average of 98%. This method was used to analyse 39 infant formula, and perchlorate concentrations ranging from

  5. Determination of total organic carbon in water by thermal combustion-ion chromatography.

    PubMed

    Fung, Y S; Wu, Z; Dao, K L

    1996-07-01

    A sensitive method for determining total organic carbon at microgram per liter levels in industrial, environmental, and drinking waters by thermal combustion ion chromatography was developed using tube furnace and readily accessable HPLC equipment. To achieve complete oxidation, persulfate (0.25%) was added to oxidize nonvolatile organic compounds in solution and cupric oxide heated at 900 °C to convert volatile organic compounds to CO(2), which was scrubbed in a 20 mL solution of 50 mM KOH with 10 drops of butanol added. The carbonate anion obtained was determined by nonsuppressed ion chromatography using 0.6 mM potassium hydrogen phthalate (KHP) as the eluent. Both surfactants and volatile and nonvolatile organic compounds commonly found in environmental waters give highly repeatable recoveries close to 100%. The detection limit (S/N = 2) and linear range for a 1 L water sample are 2 ?g of C L(-)(1) and 10-2500 ?g of C L(-)(1), respectively, and they can be adjusted using samples ranging from 100 mL to 2 L. Good repeatablity (RSD less than 10%) and close to 100% recoveries were obtained for KHP added to real samples such as deionized, mineral, tap, and river water and seawater. Compared with the ASTM D2579 method, the method developed is 3 orders of magnitude more sensitive, more accurate, and reliable in determining samples with low total organic carbon values and more flexible in adjusting the linear range and sensitivity using variable sample sizes. PMID:21619304

  6. Size Exclusion Chromatography Studies of the Initial Self-Association Steps of Chicken Egg White Lysozyme Nucleation

    NASA Technical Reports Server (NTRS)

    Ewing, Felecia; Donovan, David; Pusey, Marc

    2000-01-01

    Nucleation is one of the least understood aspects of crystallogenesis. In the case of macromolecule nucleation, this understanding is further hampered by uncertainty over what precisely is being discussed. We define the process of solute self-association (aggregation, oligomerization, interaction, clustering, etc.) whereby n-mers (n > or = 2) having a crystallographic or nascent crystallographic arrangement leading to the critical nucleus reversibly form in the solution, to be part of the nucleation process. This reversible self-association process is a fundamental part of the nucleation process, and occurs as a function of the solute concentration. In the case of chicken egg white lysozyme, a considerable body of experimental evidence leads us to the conclusion that it also forms the crystal growth units. Size exclusion chromatography is a simple and direct method for determining the equilibrium constants for the self-association process. A Pharmacia FPLC system was used to provide accurate solution flow rates. The column, injection valve, and sample loop were all mounted within a temperature-controlled chamber. Chromatographically re-purified lysozyme was first dialyzed against the column equilibration buffer, with injection onto the column after several hours pre-incubation at the running temperature. Preliminary experiments, were carried out using a Toyopearl HW-50F column (1 x 50cm), equilibrated with 0.1 M sodium acetate, 5% sodium chloride, pH 4.6, at 15C. Protein concentrations from 0.1 to 4 mg/ml were employed (C(sub sat) = 1.2 mg/ml). The data from several different protein preparations consistently shows a progressively decreasing elution volume with increasing protein concentration, indicating that reversible self-association is occurring. The dotted line indicates the monomeric lysozyme elution volume. However, lysozyme interacts with the column matrix in these experiments, which complicates data analysis.Accordingly, we are testing silica-based HPLC columns in an effort to eliminate this problem and substantially reduce the column volume and experimental run time. The results and data analysis from these and subsequent experiments will be presented.

  7. Protein identification with Liquid Chromatography and Matrix Enhanced Secondary Ion Mass Spectrometry (LC-ME-SIMS).

    PubMed

    MacAleese, Luke; Duursma, Marc C; Klerk, Leendert A; Fisher, Greg; Heeren, Ron M A

    2011-06-10

    Secondary Ion Mass Spectrometry (SIMS) is a well established method for sensitive surface atomic and molecular analysis. Protein analysis with conventional SIMS has been attempted numerous times; however it delivers exclusively fragment peaks assigned to ?-amino acids or immonium ions. In this paper we report experiments where direct sequence information could be measured thanks to a combination of HPLC separation with matrix enhanced SIMS (ME-SIMS) on tryptic digests of intact proteins. We employ peptide mass fingerprinting (PMF) and protein identification through the detection of HPLC-separated digests of Savinase (Sav.) and bovine serum albumin (BSA), followed by MASCOT search. This is the first time that the possibility of full protein identification using LC-ME-SIMS is demonstrated in a classic proteomics workflow and that a 69kDa protein is identified with SIMS. These results demonstrate both the relevance and the potential of LC-ME-SIMS in future high resolution proteomics studies. PMID:21333768

  8. Insight into the distribution of molecular weights and higher-order structure of hyaluronans and some beta-(1 --> 3)-glucans by size exclusion chromatography.

    PubMed

    Soltés, L; Mislovicová, D; Sébille, B

    1996-01-01

    The effects of high energy ultrasound and slightly raised temperature combined with the denaturing action of dimethylsulphoxide on the molecular weight and higher-order structure of hyaluronans and some beta-(1 --> 3)-glucans were studied by means of size exclusion chromatography (SEC) technique. Some experimental conditions connected with the (bio-)polymer sample preparation prior to its SEC analysis are overviewed in the light of informational relevance of studies where the action of a physical and/or chemical agent changes the hydrodynamic size of the m omolecule. PMID:8924726

  9. Determination of anions in human and animal tear fluid and blood serum by ion chromatography.

    PubMed

    Salas-Auvert, R; Colmenarez, J; de Ledo, H; Colina, M; Gutierrez, E; Bravo, A; Soto, L; Azuero, S

    1995-07-01

    An important factor contributing to the development of ion chromatography (IC) has been the need for repetitive analyses of samples with high ionic contents and samples available in microvolumes. IC was selected for the determination of Cl, NO3, SO(2-)4 and PO(3-)4 anions in tear fluid and serum from ten human volunteers of both sexes, seven young-adult black vultures (Coragyps atratus) and three young-adult chickens (Gallus gallus domesticus). The samples were analysed on a Dionex Model 2000i/SP ion-exchange chromatograph equipped with an anion guard column (Dionex IonPac AG4A), anion separator column (Dionex IonPac AS4A), suppressor column (Dionex AMMS-II) and a conductivity detector. The flow-rte of the mobile phase, 1.7 mM NaHCO3 - 1.8 mM Na2CO3 was set at 2.0 ml/min. The R.S.D. was calculated to be less than 1.5% for all anions. In the human, black vulture and chicken serum samples, the NO3, PO(3-)4 and SO(2-)4 anion contents were higher than in tears; for Cl the reverse was found. No correlation was found amongst the anion concentrations present in the tear fluid and blood serum in all samples (p > 0.05). With no sample treatment, column maintenance was required. PMID:7640773

  10. Analysis of Camellia sinensis green and black teas via ultra high performance liquid chromatography assisted by liquid-liquid partition and two-dimensional liquid chromatography (size exclusion × reversed phase).

    PubMed

    Scoparo, Camila T; de Souza, Lauro M; Dartora, Nessana; Sassaki, Guilherme L; Gorin, Philip A J; Iacomini, Marcello

    2012-01-27

    Green and black teas (Camellia sinensis) contain compounds ranging from simple phenolics to complex glycosides, many of which have well-recognized health benefits. Here, we describe two methodologies aiming to achieve a comprehensive analysis of hydro-alcoholic extracts of C. sinensis. In the first step, the extracts were partitioned in water, n-butanol, ethyl acetate and chloroform to separate the compounds according to their polarity, yielding less complex samples to be analyzed by ultra high performance liquid chromatography coupled with mass spectrometry (UHPLC-MS). Additionally, a comprehensive two dimensional liquid chromatography (2D-LC) technique, employing size exclusion chromatography (SEC) × reversed phase (BEH-C18) was developed. The following compounds were identified on the basis of retention time, UV-spectra and MS fragmentation patterns: catechins, theaflavins and their gallate derivatives; kaempferol, quercetin and myricetin mono-, di-, tri- and tetraglycosides; esters of quinic acid and gallic or hydroxycinnamic acids; purine alkaloids, such as caffeine and theobromine and many lipids. Additionally, there were many novel compounds that were previously undescribed, such as saponin isomers and gallic acid esters of four glycosides of myricetin, quercetin and kaempferol. PMID:22204932

  11. Determination of sulfur anions in spent oil shale leachates by ion chromatography

    SciTech Connect

    Niss, N.D.

    1989-07-01

    The leaching and transport of chemical constituents from spent oil shale disposal areas is an area of environmental concern at the present time. Sulfur-containing compounds are prevalent in spent oil shales and have the potential to leach into aqueous systems surrounding disposal sites. Computer modeling has been used in recent years to predict the transport of species in an aqueous environment. The quality of model predictions, however, depends on the validation steps taken in comparing model predictions with laboratory data on ion speciation. Further, the quality of the validation step depends on the reliability of laboratory methods in generating ion speciation data. The purpose of this study was to develop methods to separate and quantify sulfur-containing anions in spent oil shale leachates by suppressed ion chromatography. The anions studied were S{sup 2{minus}} (sulfide), SO{sup 2{minus}}{sub 3} (sulfite), SO{sup 2{minus}}{sub 4} (sulfate), SCN{sup {minus}} (thiocyanate), S{sub 2}O{sup 2{minus}}{sub 3} (thiosulfate), and S{sub 4}O{sup 2{minus}}{sub 6} (tetrathionate). After the separations were developed, a series of method-challenging experiments were performed to test the reliability of the methods and assure the development of an analytically sound product. 24 refs., 7 figs., 5 tabs.

  12. [Determination of piperidinium ionic liquid cations by ion-pair chromatography-indirect ultraviolet detection].

    PubMed

    Wang, Miaoyu; Yu, Hong; Li, Ping; Li, Jie; Gao, Yufeng

    2014-07-01

    A method was developed for the determination of piperidinium cations by ion-pair chromatography with indirect ultraviolet detection. Chromatographic separation was performed on a reversed-phase C18 column using background ultraviolet absorption reagent-ion-pair reagent/organic solvent as mobile phase. The effects of the background ultraviolet absorption reagent, detection wavelength, ion-pair reagent, organic solvent, column temperature and flow rate on the determination of piperidinium cations were investigated and the retention rules were studied. The optimized chromatographic conditions for the determination of piperidinium cations were as follows: mobile phase, 0.5 mmol/L 4-aminophenol hydrochloride-0.1 mmol/L 1-heptanesulfonic acid sodium aqueous solution/methanol (80:20, v/v); detection wavelength, 210 nm; column temperature, 30 degrees C; flow rate, 1.0 mL/min. Under these conditions, the three piperidinium cations were baseline separated within 4 min. The detection limits (S/N = 3) of the piperidinium cations were 0.137-0.545 mg/L. The relative standard deviations (n = 5) for peak area and retention time were 0.72% and 0.37% respectively. The method has been successfully applied to the determination of piperidinium cations in ionic liquids synthesized by chemistry laboratory. The recoveries of piperidinium cations after spiking were 97.0%-98.4%. The method is simple, rapid, reproducible, linear, and can meet the quantitative analysis requirement for the determination of piperidinium cations. PMID:25255572

  13. Efficient separation of acetate and formate by ion chromatography: Application to air samples in a cultural heritage environment

    Microsoft Academic Search

    Velichka Kontozova-Deutsch; Agnieszka Krata; Felix Deutsch; László Bencs; René Van Grieken

    2008-01-01

    A method for the separation of acetate and formate anions by ion chromatography has been optimized under various measurement conditions (e.g. the composition of the mobile phase, and the flow rate of the eluent). For this purpose, two different analytical columns were examined: the IonPac AS14 (250mm×4mm i.d.; designed mostly for the separation of inorganic anions) and the Allsep A-2

  14. Combining size-exclusion chromatography and fully automated chip-based nanoelectrospray quadrupole time-of-flight tandem mass spectrometry for structural analysis of chondroitin/dermatan sulfate in human decorin.

    PubMed

    Zamfir, Alina D; Flangea, Corina; Sisu, Eugen; Seidler, Daniela G; Peter-Katalini?, Jasna

    2011-06-01

    Chondroitin/dermatan sulfate (CS/DS) chain of decorin (DCN) from human skin fibroblasts (HSk) was released by reductive ?-elimination reaction and digested with chondroitin AC I lyase. Enzymatic hydrolysis mixture of CS/DS chains was separated by size-exclusion chromatography (SEC). Collected octasaccharide fraction was subjected to fully automated chip-based nanoelectrospray (nanoESI) quadrupole time-of-flight (QTOF) MS and tandem MS (MS/MS). MS of human skin fibroblasts DCN CS/DS displayed a high complexity due to the large variety of glycoforms, which under chip-nanoESI MS readily ionized to form multiply charged ions. Except for the regularly tetrasulfated octasaccharide, the investigated fraction contained four additional octasaccharides of atypical sulfation status. Two new oversulfated glycoforms and two undersulfated species were identified. Remarkably, the series of decasaccharides discovered in the same SEC pool was found to encompass a trisulfated and a novel hexasulfated [4,5-?-GlcAGalNAc(IdoAGalNAc)?] species. MS/MS by collision-induced dissociation (CID) on the [M-4H]? ion corresponding to the previously not reported [4,5-?-GlcAGalNAc(IdoAGalNAc)?](5S) corroborated for a novel motif in which three N-acetylgalactosamine (GalNAc) moieties are monosulfated, 4,5-?-GlcA and the first IdoA from the non-reducing end bear one sulfate group each, while the second N-acetylgalactosamine from the reducing end is unsulfated. PMID:21647927

  15. [Determination of eleven preservatives including bronopol in cosmetic by reversed-phase ion-pair chromatography].

    PubMed

    Hu, J; Wang, J

    1999-09-01

    Reversed-phase ion-pair chromatography was used to detect 11 preservatives including bronopol, esters of p-hydroxybenzoic acid (PHBA) in cosmetics. Zorbax C8 column was used and mobile phase was V (0.05 mol/L NaH2PO4):V(methyl alcohol):V(acetonitrile) = 50:35:15 with addition of hexadecyltrimethylammonium chloride (2 mmol/L) and the pH adjusted to 3.5 by using phosphoric acid. The wavelength 254 nm was selected for detection. Samples were extracted with methanol by ultrasonic method. The recoveries were 85%-107% and the relative standard deviations were 2.2%-7.5%. PMID:12552895

  16. Modeling of ion exchange expanded-bed chromatography for the purification of C-phycocyanin.

    PubMed

    Moraes, Caroline Costa; Mazutti, Marcio A; Maugeri, Francisco; Kalil, Susana Juliano

    2013-03-15

    This work is focused on the experimental evaluation and mathematical modeling of ion exchange expanded-bed chromatography for the purification of C-phycocyanin from crude fermentative broth containing Spirulina platensis cells. Experiments were carried out in different expansion degree to evaluate the process performance. The experimental breakthrough curves were used to estimate the mass transfer and kinetics parameters of the proposed model, using the Particle Swarm Optimization algorithm (PSO). The proposed model satisfactorily fitted the experimental data. The results from the model application pointed out that the increase in the initial bed height does not influence the process efficiency, however enables the operation of expanded-bed column at high volumetric flow rates, improving the productivity. It was also shown that the use of mathematical modeling was a good and promising tool for the optimization of chromatographic processes. PMID:23411140

  17. Isotope effects of neodymium in different ligands exchange systems studied by ion exchange displacement chromatography

    PubMed Central

    Ismail, Ibrahim; Fawzy, Ahmed S.; Ahmad, Mohammad I.; Aly, Hisham F.; Nomura, Masao; Fujii, Yasuhiko

    2012-01-01

    The isotope effects of neodymium in Nd-glycolate ligand exchange system were studied by using ion exchange chromatography. The separation coefficients of neodymium isotopes, ?’s, were calculated from the observed isotopic ratios at the front and rear boundaries of the neodymium adsorption band. The values of separation coefficients of neodymium isotopes, ?’s, for the Nd-glycolate ligand exchange system were compared with those of Nd-malate and Nd-citrate, which indicated that the isotope effects of neodymium as studied by the three ligands takes the following direction Malate > Citrate > Glycolate. This order agrees with the number of available sites for complexation of each ligand. The values of the plate height, HETP of Nd in Nd-ligand exchange systems were also calculated. PMID:25685410

  18. Isotope effects of neodymium in different ligands exchange systems studied by ion exchange displacement chromatography.

    PubMed

    Ismail, Ibrahim; Fawzy, Ahmed S; Ahmad, Mohammad I; Aly, Hisham F; Nomura, Masao; Fujii, Yasuhiko

    2013-03-01

    The isotope effects of neodymium in Nd-glycolate ligand exchange system were studied by using ion exchange chromatography. The separation coefficients of neodymium isotopes, ?'s, were calculated from the observed isotopic ratios at the front and rear boundaries of the neodymium adsorption band. The values of separation coefficients of neodymium isotopes, ?'s, for the Nd-glycolate ligand exchange system were compared with those of Nd-malate and Nd-citrate, which indicated that the isotope effects of neodymium as studied by the three ligands takes the following direction Malate > Citrate > Glycolate. This order agrees with the number of available sites for complexation of each ligand. The values of the plate height, HETP of Nd in Nd-ligand exchange systems were also calculated. PMID:25685410

  19. Monitoring of Lactobacillus fermentation process by using ion chromatography with a series piezoelectric quartz crystal detector.

    PubMed

    Zhang, J; Xie, Y; Dai, X; Wei, W

    2001-03-01

    A new method monitoring Lactobacillus fermentation process, which combines ion chromatography (IC) with a series piezoelectric quartz crystal (SPQC) technique, is presented in this paper. Monitoring of the fermentation process was realized by examining the rate of production of lactic acid. An automatic membrane dialyser was used for the pretreatment of the sample in on-line monitoring. A mixture of p-hydroxybenzoic acid and N,N-diethylethanolamine was adopted as mobile phase and its flow rate was 0.8 ml/min. The effects of some fermentation conditions were also discussed in detail. Accordingly, the optimal fermentation conditions were obtained. This method is simple and convenient while the results obtained are accurate and reliable. PMID:11165339

  20. Chloride determination by ion chromatography in petroleum coke after digestion by microwave-induced combustion.

    PubMed

    Pereira, Juliana S F; Diehl, Liange O; Duarte, Fábio A; Santos, Maria F P; Guimarães, Regina C L; Dressler, Valderi L; Flores, Erico M M

    2008-12-12

    Microwave-induced combustion was applied to petroleum coke digestion in closed vessels for further chloride determination by ion chromatography. Samples were pressed as pellets and placed on a quartz holder. Combustion was performed using oxygen pressure of 2 MPa and 50 microl of 6 moll(-1) NH(4)NO(3) as aid for ignition. Recoveries from 97 to 102% were obtained for all studied absorbing solutions (water, H(2)O(2), Na(2)CO(3) or (NH(4))(2)CO(3)). Accuracy was evaluated using certified reference materials with agreement better than 98% using water as absorbing solution with reflux step. The limit of quantification was 3.8 microg g(-1). PMID:18996537

  1. Ion chromatography applications in the determination of HF, HCl, NOx, SOx on stationary emissions.

    PubMed

    Giuriati, Caterina; Cristofori, Maria Cristina; Gorni, Alfredo; Abballe, Franco

    2003-01-01

    In this work, specific topics will be covered in order to verify an effective, routine application of ion chromatography as a suitable and approved technique for emission monitoring in the determination of HF, HCl, NOx and SOx on stationary emission. A review of the analytical methods as proposed by recent updates in Italian environmental law and the problems encountered in the application of this method, such us the interference due to high level of carbonate, high hydroxides concentration particularly on SOx and NOx absorbing solution, are considered in the present work. The sample treatments before the IC analysis, this to reduce the matrix interference due to the strong basic solutions used to monitor different stationary emissions, are also examined. Some modifications in sampling are explored to find more suitable conditions for the IC analysis. PMID:14587221

  2. Effect of eluent composition on retention behavior of anions in ion chromatography on anion-exchangers modified with heparin

    Microsoft Academic Search

    Safni; Toyohide Takeuchi; Tomoo Miwa; Yoshimi Hashimoto; Hiroyuki Moriyama

    1999-01-01

    Effects of eluent composition on retention behavior of inorganic anions have been investigated in ion chromatography using anion-exchangers modified with heparin. Both cation and anion of the eluent affected the retention of analyte anions and unusual retention behavior was observed on the modified stationary phase. The retention time of anions decreased with decreasing eluent concentration when sodium sulfate, magnesium sulfate

  3. SPECIATION OF SELENIUM(IV) AND SELENIUM(VI) USING COUPLED ION CHROMATOGRAPHY: HYDRIDE GENERATION ATOMIC ABSORPTION SPECTROMETRY

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A simple method was developed to speciate inorganic selenium in the microgram per liter range using coupled ion chromatography-hydride generation atomic absorption spectrometry. Because of the differences in toxicity and adsorption behavior, determination of the redox states selenite, Se(IV), and s...

  4. Determination of total sulfur by ion chromatography following peroxide oxidation in spent caustic from the chemical cleaning of coal

    Microsoft Academic Search

    Colin D. Chriswell; David R. Mroch; Richard. Markuszewski

    1986-01-01

    Total sulfur in samples of spent caustic arising from the chemical cleaning of coal has been determined by ion chromatography after oxidation of all sulfur species to sulfate. Oxidation with hydrogen peroxide first under basic conditions and subsequently under strongly acidic conditions was required for quantitative conversion of all sulfur species to sulfate. The effects of pH, sample size, and

  5. Quantification of iodide and sodium-iodide symporter inhibitors in human urine using ion chromatography tandem mass spectrometry

    Microsoft Academic Search

    Liza Valentín-Blasini; Benjamin C. Blount; Amy Delinsky

    2007-01-01

    We developed a sensitive and selective method for quantifying nitrate, thiocyanate, perchlorate and iodide in human urine using ion chromatography coupled with electrospray ionization tandem mass spectrometry. Analysis of proficiency testing materials and spiked urine indicates that the method is precise (coefficients of variation 99% of urine samples tested. Measurement of these four toxicologically-related analytes in one assay will provide

  6. Simultaneous and sensitive analysis of aliphatic carboxylic acids by ion-chromatography using on-line complexation with copper(II) ion.

    PubMed

    Kemmei, Tomoko; Kodama, Shuji; Yamamoto, Atsushi; Inoue, Yoshinori; Hayakawa, Kazuichi

    2015-01-01

    A new approach to ion chromatography is proposed to improve the UV detection of aliphatic carboxylic acids separated by anion-exchange chromatography. When copper(II) ion added to the mobile phase, it forms complexes with carboxylic acids that can be detected at 240 nm. The absorbance was found to increase with increasing copper(II) ion concentration. The retention times of ?-hydroxy acids were also found to depend on the copper(II) ion concentration. Addition of acetonitrile to the mobile phase improved the separation of aliphatic carboxylic acids. The detection limits of the examined carboxylic acids (formate, glycolate, acetate, lactate, propionate, 3-hydroxypropionate, n-butyrate, isobutyrate, n-valerate, isovalerate, n-caproate) calculated at S/N=3 ranged from 0.06 to 3 ?M. The detector signal was linear over three orders of magnitude of carboxylic acid concentration. The proposed method was successfully applied to analyze aliphatic carboxylic acids in rainwater and bread. PMID:25523885

  7. Scaled-up separation of cellobiohydrolase1 from a cellulase mixture by ion-exchange chromatography.

    PubMed

    Ye, Zhuoliang; Lane, Andrew N; Willing, Gerold A; Berson, R Eric

    2011-01-01

    Enzymatic hydrolysis of cellulose often involves cellulases produced by Trichoderma reesei, of which cellobiohydrolase1 (CBH1) is the most abundant (about 60% of total cellulases) and plays an important role in the hydrolysis of crystalline cellulose. A method for separating sufficient quantities from the bulk cellulase cocktail is highly desirable for many studies, such as those that aim to characterize binding and hydrolysis kinetics of CBH1. In this work, CBH1 was separated from other Spezyme CP cellulases by ion-exchange chromatography using an efficient modification of a smaller scale process. The ion-exchange column was connected to a vacuum manifold system to provide a steady flow through parallel columns and thus achieve scale-up for enzyme separation. With five 5-mL columns running in parallel, about 55 mg of CBH1 was separated from 145 mg of Spezyme CP in a single separation. Step elution was used to replace the continuous gradient used at smaller scale. The purified CBH1 was collected in the fraction eluted with a buffer containing 0.33 M salt and showed comparable purity and activity as the enzyme purified by a fast protein liquid chromatography system. The stability of separated CBH1 was studied for up to 2 days and good thermal stability was observed. Separated CBH1 also showed both high adsorption to bacterial microcrystalline cellulose with ~4 ?mol/g maximum adsorption and a K(a) of 5.55 ± 2.34 ?M(-1) , and good hydrolytic activity based on atomic force microscopy observations that show a reduction in fiber height. PMID:21905272

  8. DIONEX ICS3000 ION CHROMATOGRAPHY SYSTEM INSTALLATION AND INSTRUMENT ASSESSMENT FOR SRNL APPLICATIONS

    SciTech Connect

    Wiedenman, B.; White, T.

    2009-11-16

    Ion Chromatography (IC) is routinely used at the Savannah River National Laboratory (SRNL) for sample analysis and characterization. Results from IC analysis are valued in corrosion control maintenance and measurement programs, remediation waste process control, soil and ground water measurement, nuclear materials processing, and various other research and development programs. Presented in this report are analytical methods developed on a DIONEX ICS3000 Reagent Free Ion Chromatography (RFIC) system located in AD at SRNL. This IC system contains two independent analysis channels comprising of a mobile phase generator, a pump, stationary phase columns, a suppressor and a conductivity detector. One channel is dedicated to anion analysis using Potassium Hydroxide (KOH) as the mobile phase while a second channel is configured for cation analysis using Methanesulfonic Acid (MSA) as the mobile phase. Both channels share an autosampler and the peak analysis software, Chromeleon{reg_sign} v.6.8. Instrument configuration is modified from the manufacturer for radiological service. Listed within this report are Dionex ICS3000 parameters and results for the analysis of routine anions and cations. Additional method parameters and discussion are presented on the analysis of Acetate (CH{sub 3}COO{sup -}) and Iodate (IO{sub 3}{sup -}). Previous IC analysis instruments at AD have been based upon carbonate/bicarbonate buffer mobile phase chemistry. This report represents a transition to hydroxide as a mobile phase eluent. The hydroxide eluent offers a lower baseline conductivity, which allows for greater sample dilution and/or lower detection limits. Also the hydroxide mobile phase and column set has a significant separation of the phosphate peak from the nitrate and sulfate peaks vs. the carbonate/bicarbonate mobile phase and column set, an advantage for the industrial waste analyzed at SRNL.

  9. Identification and quantification of glucosinolates in rapeseed using liquid chromatography-ion trap mass spectrometry.

    PubMed

    Millán, Silvia; Sampedro, M Carmen; Gallejones, Patricia; Castellón, Ander; Ibargoitia, Maria L; Goicolea, M Aranzazu; Barrio, Ramón J

    2009-07-01

    A rapid and sensitive method for the speciation and quantification of glucosinolates in rapeseed is described. The method combines liquid chromatography (LC) with ion trap mass spectrometry (ITMS) detection. Electrospray ionization (ESI) has been chosen as the ionization technique for the on-line coupling of LC with ITMS. Glucosinolates are extracted from different rapeseeds with MeOH and the extracts are cleaned-up by solid phase extraction with Florisil cartridges. Aqueous extracts are injected into LC system coupled to an ITMS, leading to accurately quantify eight of the most important glucosinolates in rapeseed, by MS2 mode and confirming their structure by MS3 acquisition. All the glucosinolates found in rapeseeds provide good signals corresponding to the deprotonated precursor ion [M-H]-. The method is reliable and reproducible, and detection limits range from 0.5 nmol g(-1) to 3.7 nmol g(-1) when 200 mg of dried seeds of certified reference material are analyzed. Within-day and between-day RSD percentages range between 2.4-14.1% and 3.9-16.9%, respectively. The LC-ESI-ITMS-MS method described here allows for a rapid assessment of these metabolites in rapeseed without a desulfatation step. The overall process has been successfully applied to identify and quantify glucosinolates in rapeseed samples. PMID:19430963

  10. Collection of ethanolamines in air and determination by mobile phase ion chromatography

    SciTech Connect

    Bouyoucos, S.A.; Melcher, R.G.

    1986-03-01

    A method is described for the collection and determination of monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA) in air. Samples were collected by pulling air through a glass tube containing alumina, cleaned especially to remove interfering inorganic ions. The ethanolamines were desorbed with water and determined by Mobile Phase Ion Chromatography (MPIC). The recovery and total relative precision for MEA, DEA, and TEA - all collected from air at a flow rate of 100 mL/min for 7 hr - was 93.1 +/- 17%, 92.7 +/- 15% and 89.4 +/- 21%, respectively (95% confidence level). The method was validated for all three compounds from approximately the limit of detection (3 x noise) to ten times the limit of detection. Based on a sample size of 42 L, MEA was validated over the range from 0.12 to 3.0 ppm v/v (TLV=3), DEA over the range from 0.25 to 3.3 ppm v/v (TLV=3) and TEA from 0.31 to 3.7 ppm v/v (no TLV assigned). No effect on recovery was observed when sampling at high humidity or on storage of the samples for up to 31 days.

  11. Ion-pair liquid chromatography--atmospheric pressure ionization mass spectrometry for the determination of quaternary ammonium herbicides.

    PubMed

    Castro, R; Moyano, E; Galceran, M T

    1999-01-01

    High-performance liquid chromatography coupled with atmospheric pressure ionization mass spectrometry (electrospray and atmospheric pressure chemical ionization) has been used to characterize some quaternary ammonium herbicides (quats). The separation of these compounds was carried out using ion-pair chromatography with heptafluorobutyric acid (15 mM, pH 3.3) and acetonitrile gradient elution for successful coupling to mass spectrometry. Detection limits down to 0.1-4 micrograms l-1 were obtained for spiked tap water following a preconcentration step. Good reproducibilities (day-to-day and run-to-run) were also obtained. PMID:10023623

  12. Quality control considerations for size exclusion chromatography with online ICP-MS: a powerful tool for evaluating the size dependence of metal-organic matter complexation

    PubMed Central

    McKenzie, Erica R.; Young, Thomas M.

    2013-01-01

    Size exclusion chromatography (SEC), which separates molecules based on molecular volume, can be coupled with online inductively coupled plasma mass spectrometry (ICP-MS) to explore size-dependent metal-natural organic matter (NOM) complexation. To make effective use of this analytical dual detector system, the operator should be mindful of quality control measures. Al, Cr, Fe, Se, and Sn all exhibited columnless attenuation, which indicated unintended interactions with system components. Based on signal-to-noise ratio and peak reproducibility between duplicate analyses of environmental samples, consistent peak time and height were observed for Mg, Cl, Mn, Cu, Br, and Pb. Al, V, Fe, Co, Ni, Zn, Se, Cd, Sn, and Sb were less consistent overall, but produced consistent measurements in select samples. Ultrafiltering and centrifuging produced similar peak distributions, but glass fiber filtration produced more high molecular weight peaks. Storage in glass also produced more high molecular weight peaks than did plastic bottles. PMID:23416600

  13. Combined Protein A and size exclusion high performance liquid chromatography for the single-step measurement of mAb, aggregates and host cell proteins.

    PubMed

    Gjoka, Xhorxhi; Schofield, Mark; Cvetkovic, Aleksandar; Gantier, Rene

    2014-12-01

    Quantification of monoclonal antibody (mAb) monomer, mAb aggregates, and host cell proteins (HCPs) is critical for the optimization of the mAb production process. The present work describes a single high throughput analytical tool capable of tracking the concentration of mAb, mAb aggregate and HCPs in a growing cell culture batch. By combining two analytical HPLC methods, Protein A affinity and size-exclusion chromatography (SEC), it is possible to detect a relative increase or decrease in the concentration of all three entities simultaneously. A comparison of the combined Protein A-SEC assay to SEC alone was performed, demonstrating that it can be useful tool for the quantification of mAb monomer along with trending data for mAb aggregate and HCP. Furthermore, the study shows that the Protein A-SEC method is at least as accurate as other commonly used analytical methods such as ELISA and Bradford. PMID:25310707

  14. Size Exclusion High Performance Liquid Chromatography: Re-Discovery of a Rapid and Versatile Method for Clean-Up and Fractionation in Chemical Ecology.

    PubMed

    Sperling, Sergej; Kühbandner, Stephan; Engel, Katharina C; Steiger, Sandra; Stökl, Johannes; Ruther, Joachim

    2015-06-01

    Solvent extraction of bioactive molecules from glands, tissues, or whole organisms is a common first step in chemoecological studies. Co-extraction of a surplus of high boiling materials such as triacylglycerides (TAGs) and other lipids with higher molecular weight might hamper the identification of volatile or medium-volatile semiochemicals by high resolution chromatographic and spectroscopic techniques. Therefore, effective clean-up procedures are needed to separate potential semiochemicals from the accompanying materials. Size exclusion high performance liquid chromatography (SE-HPLC), a technique often disregarded by chemoecologists, has proved to be a rapid and efficient clean-up method for complex crude extracts. We demonstrated that TAGs can be baseline separated from typical semiochemicals within less than 10 min on a porous gel stationary phase based on highly cross-linked polystyrene/divinylbenzene. We applied the method as a rapid one-step clean-up procedure for the analysis of juvenile hormone III in insect hemolymph by gas chromatography-mass spectrometry. We furthermore introduced some recent application examples on insect pheromones to demonstrate that SE-HPLC is not only an effective method for the purification of crude extracts, but can as well be used as a first fractionation step for the bioassay-guided identification of behavior modifying natural products. SE-HPLC can be well operated with low-boiling solvents such as dichloromethane, and results in fraction volumes of typically less than one ml, which decreases the danger of losing volatile analytes during subsequent concentration steps. PMID:25943862

  15. Online stable isotope analysis of dissolved organic carbon size classes using size exclusion chromatography coupled to an isotope ratio mass spectrometer.

    PubMed

    Malik, Ashish; Scheibe, Andrea; LokaBharathi, P A; Gleixner, Gerd

    2012-09-18

    Stable isotopic content of dissolved organic carbon (?(13)C-DOC) provides valuable information on its origin and fate. In an attempt to get additional insights into DOC cycling, we developed a method for ?(13)C measurement of DOC size classes by coupling high-performance liquid chromatography (HPLC)-size exclusion chromatography (SEC) to online isotope ratio mass spectrometry (IRMS). This represents a significant methodological contribution to DOC research. The interface was evaluated using various organic compounds, thoroughly tested with soil-water from a C3-C4 vegetation change experiment, and also applied to riverine and marine DOC. ?(13)C analysis of standard compounds resulted in excellent analytical precision (?0.3‰). Chromatography resolved soil DOC into 3 fractions: high molecular weight (HMW; 0.4-10 kDa), low molecular weight (LMW; 50-400 Da), and retained (R) fraction. Sample reproducibility for measurement of ?(13)C-DOC size classes was ±0.25‰ for HMW fraction, ± 0.54‰ for LMW fraction, and ±1.3‰ for R fraction. The greater variance in ?(13)C values of the latter fractions was due to their lower concentrations. The limit of quantification (SD ?0.6‰) for each size fraction measured as a peak is 200 ng C (2 mg C/L). ?(13)C-DOC values obtained in SEC mode correlated significantly with those obtained without column in the ?EA mode (p < 0.001, intercept 0.17‰), which rules out SEC-associated isotopic effects or DOC loss. In the vegetation change experiment, fractions revealed a clear trend in plant contribution to DOC; those in deeper soils and smaller size fractions had less plant material. It was also demonstrated that the technique can be successfully applied to marine and riverine DOC without further sample pretreatment. PMID:22861907

  16. Direct coupling of packed column supercritical fluid chromatography to continuous corona discharge ion mobility spectrometry.

    PubMed

    Rahmanian, A; Ghaziaskar, H S; Khayamian, T

    2013-01-11

    In this study, packed column supercritical fluid chromatography (SFC) was directly coupled to a continuous corona discharge (CD) ion mobility spectrometer (IMS) with several modifications. The main advantage of the developed detector is its capability to introduce full column effluent up to 2000 mL min(-1) CO(2) gas directly into the IMS cell relative to 40 mL min(-1) CO(2) gas as a maximum tolerance, reported for the previous IMS detectors. This achievement was made possible because of using corona discharge instead of (63)Ni as an ionization source and locating the inlet and outlet of the CO(2) gas in the counter electrode of the CD in opposite direction. In addition, a heated interface was placed between back pressure regulator (BPR) and the IMS cell to heat the output of the BPR for introducing sample as the gas phase into the IMS cell. Furthermore, a make-up methanol flow was introduced between the column outlet and BPR to provide a more uniform flow through the BPR and also to prevent freezing and deposition of the analytes in the BPR. The performance of the SFC-CD-IMS was evaluated by analysis of testosterone, medroxyprogesterone, caffeine, and theophylline as test compounds and figures of merit for these compounds have been calculated. PMID:23261285

  17. Simultaneous determination of trace oxyhalides and haloacetic acids using suppressed ion chromatography-electrospray mass spectrometry.

    PubMed

    Barron, Leon; Paull, Brett

    2006-05-15

    A new analytical procedure for the simultaneous determination of trace oxyhalides and haloacetic acids (HAs) in drinking water and aqueous soil extracts is described. The method uses micro-bore ion chromatography (IC) coupled with suppressed conductivity (SC) and electrospray ionization mass spectrometric detection (ESI-MS). The IC-SC-ESI-MS system included a secondary flow of 100% MeOH, which was added to the column eluate (post-suppressor) and resulted in a significant increase in sensitivity for all analytes. All ESI-MS parameters were optimized for HA analysis and sensitivity quantitatively compared to suppressed conductivity. Full analytical performance characteristics for the developed method are presented for monochloro-, monobromo-, dichloro-, dibromo-, trichloro-, bromochloro, chlorodifluoro-, trifluoro-, dichlorobromo- and dibromochloroacetic acid, as well as the oxyhalides iodate, bromate, chlorate and perchlorate. In the case of the HAs, an optimised 25-fold SPE preconcentration method meant all analytes could be readily detected well below the USEPA 60mug/L regulatory limit using conductivity and/or ESI-MS. The IC-ESI-MS method was applied to the determination of oxyhalides and HAs in both soil extracts and drinking water samples. Soil samples were extracted using ultra pure water with subsequent determination of perchlorate at 1.68mug/g of soil. A drinking water sample containing HAs was preconcentrated using LiChrolut EN solid phase extraction cartridges with subsequent sulphate and chloride removal. Total HAs were determined at 13mug/L. PMID:18970613

  18. Determination of beryllium in a stream sediment by high-performance chelation ion chromatography.

    PubMed

    Shaw, M J; Hill, S J; Jones, P; Nesterenko, P N

    2000-04-21

    High-performance chelation ion chromatography (HPCIC), involving a chelating silica substrate bonded with aminomethylphosphonic acid, has been developed as a novel technique for the quantitative determination of beryllium in complex matrices. An isocratic separation method, using an eluent containing 1 M KNO3, 0.5 M HNO3 and 0.08 M ascorbic acid, allowed the Be2+ to elute away from the sample matrix peak in under 6 min in a sample containing in excess of 800 mg l(-1) matrix metals. A detection limit of 35 microg l(-1) Be(II) was found using a post-column reaction involving Chrome Azurol S (CAS), 1 M hexamine and 10 mM EDTA buffered at pH 6. The standard addition curve gave excellent linearity (R2>0.999). The procedure was applied to the determination of trace beryllium in a certified sediment sample. The results obtained compared well with the certified value for beryllium. PMID:10823508

  19. The analysis of black powder substitutes containing ascorbic acid by ion chromatography/mass spectrometry.

    PubMed

    Lang, Gui-hua Lisa; Boyle, Katherine M

    2009-11-01

    Black powder substitutes containing ascorbic acid are a group of low explosives that utilize ascorbic acid as the fuel. The analysis of these powders is complicated by the degradation of ascorbic acid which occurs rapidly in solution and may also occur as the powder ages. Aqueous extracts of both intact powders and postblast residues were analyzed by an existing ion chromatography/mass spectrometry (IC/MS) method used at the Bureau of Alcohol, Tobacco, Firearms and Explosives. Results have shown that while ascorbic acid itself is not detected in this method, its diagnostic degradation products (threonic acid, monohydrated diketogulonic acid, and oxalic acid) can be identified. In addition, anions from the inorganic oxidizers (perchlorate and nitrate) and combustion products such as chloride, chlorate, and nitrite, can be identified within the same experiment. While this IC/MS method shows promise, future modifications are necessary because of limitations in identifying threonate in postblast residues, as well as coeluting compounds observed in postblast residues. PMID:19732276

  20. ANION ANALYSES BY ION CHROMATOGRAPHY FOR THE ALTERNATE REDUCTANT DEMONSTRATION FOR THE DEFENSE WASTE PROCESSING FACILITY

    SciTech Connect

    Best, D.

    2010-08-04

    The Process Science Analytical Laboratory (PSAL) at the Savannah River National Laboratory was requested by the Defense Waste Processing Facility (DWPF) to develop and demonstrate an Ion Chromatography (IC) method for the analysis of glycolate, in addition to eight other anions (fluoride, formate, chloride, nitrite, nitrate, sulfate, oxalate and phosphate) in Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) samples. The method will be used to analyze anions for samples generated from the Alternate Reductant Demonstrations to be performed for the DWPF at the Aiken County Technology Laboratory (ACTL). The method is specific to the characterization of anions in the simulant flowsheet work. Additional work will be needed for the analyses of anions in radiological samples by Analytical Development (AD) and DWPF. The documentation of the development and demonstration of the method fulfills the third requirement in the TTQAP, SRNL-RP-2010-00105, 'Task Technical and Quality Assurance Plan for Glycolic-Formic Acid Flowsheet Development, Definition and Demonstrations Tasks 1-3'.

  1. Application of high-performance ion-exchange chromatography to the analysis of cytosolic glucocorticoid receptor.

    PubMed

    Denis, M; Guendouz, F; Blanchardie, P; Bernard, S; Lustenberger, P

    1988-01-01

    The use of high-performance ion-exchange chromatography (HPIEC) on a Mono Q column was investigated for the analysis of glucocorticoid receptor. In the presence of 10 mM sodium molybdate, both liganded and unliganded glucocorticoid receptor were eluted as a single and sharp peak (0.32 M NaCl). In the absence of molybdate and after exposure to heat and salt, another peak of specifically bound radioactivity was eluted with 0.08 M NaCl. When HPIEC was performed in the absence of molybdate, two molecular forms of the liganded receptor were detected which eluted with 0.08 M NaCl (Stokes' radius Rs = 5.1 nm, s20,w = 4.6 S, calculated mol. wt Mr approximately 100,000) and 0.32 M NaCl (Rs = 7.3 nm, S20,w = 9.0 S, calculated Mr approximately 280,000). Analysis of both forms with mini-columns of DNA-Ultrogel, DEAE-Trisacryl and hydroxylapatite (HA-Ultrogel) confirmed the identity of the two peaks with transformed and non-transformed glucocorticoid-receptor complexes. These results suggest that HPIEC may provide a useful tool for the rapid resolution and quantification of receptor molecular forms. PMID:3386254

  2. Anionic forensic signatures for sample matching of potassium cyanide using high performance ion chromatography and chemometrics.

    PubMed

    Fraga, Carlos G; Farmer, Orville T; Carman, April J

    2011-01-30

    Potassium cyanide was used as a model toxicant to determine the feasibility of using anionic impurities as a forensic signature for matching cyanide salts back to their source. In this study, portions of eight KCN stocks originating from four countries were separately dissolved in water and analyzed by high performance ion chromatography (HPIC) using an anion exchange column and conductivity detection. Sixty KCN aqueous samples were produced from the eight stocks and analyzed for 11 anionic impurities. Hierarchal cluster analysis and principal component analysis were used to demonstrate that KCN samples cluster according to source based on the concentrations of their anionic impurities. The Fisher-ratio method and degree-of-class separation (DCS) were used for feature selection on a training set of KCN samples in order to optimize sample clustering. The optimal subset of anions needed for sample classification was determined to be sulfate, oxalate, phosphate, and an unknown anion named unk5. Using K-nearest neighbors (KNN) and the optimal subset of anions, KCN test samples from different KCN stocks were correctly determined to be manufactured in the United States. In addition, KCN samples from stocks manufactured in Belgium, Germany, and the Czech Republic were all correctly matched back to their original stocks because each stock had a unique anionic impurity profile. The application of the Fisher-ratio method and DCS for feature selection improved the accuracy and confidence of sample classification by KNN. PMID:21215851

  3. Gas chromatography-mass spectrometry/selected ion monitoring for screening asymmetric epoxidation of styrene.

    PubMed

    Mu, Yao; Wei, Siping; Xu, Min; Chen, Ping; Wang, Qin; Du, Xi

    2014-12-01

    A screening method by gas chromatography-mass spectrometry (GC-MS) with selected ion monitoring (SIM) has been developed for asymmetric epoxidation of styrene. All samples were analyzed by GC-MS with the mode of SIM by using ethylbenzene as the internal standard, by which styrene and styrene epoxide enantiomers were completely separated and their concentrations were accurately determined. Furthermore, this method was used to evaluate the epoxidation reaction of styrene, which was optimized by orthogonal experiment. The advantages of the method are as follows: excellent precision (RSD in the range of 1. 2% - 5. 2%, n= 5), good linearity (the correlation coefficients for styrene, (R)/(S)-styrene oxide were 0. 9997, 0. 9932 and 0. 9963, respectively) , low limits of quantitation (LOQs of styrene, (R)/(S)-styrene oxide were 1. 3, 1. 1 and 0. 7 mg/L, respectively) and reasonable recoveries (98. 2% - 108. 2%). All in all, the method provided a new way to determine the asymmetric epoxidation mixture of styrene and its homologs. PMID:25902648

  4. A Volatile Organic Analyzer for Space Station - Description and evaluation of a gas chromatography\\/ion mobility spectrometer

    Microsoft Academic Search

    Thomas Limero; John Brokenshire; Colin Cumming; Ed Overton; Ken Carney; Jay Cross; Gary Eiceman; John James

    1992-01-01

    An on-board Volatile Organic Analyzer (VOA), an essential component of the Environmental Health System (EHS) air-quality monitoring strategy, is described. The strategy is aimed at warning the crew and ground personnel if volatile compounds exceed safe exposure limits. The VOA uses a combination of gas chromatography (GC) and ion-mobility spectrometry (IMS) for environmental monitoring and analysis. It is concluded that

  5. Determination of Tertiary-butylhydroquinone and Its Metabolites in Rat Serum by Liquid Chromatography–Ion Trap Mass Spectrometry

    Microsoft Academic Search

    Wen Huang; Yinchun Gu; Hai Niu

    2008-01-01

    A new method applying sensitive and selective liquid chromatography coupled with mass spectrometry (LC\\/MS\\/MS) for analyzing\\u000a tertiary-butylhydroquinone (TBHQ) and its metabolites in rat serum was validated. Using an extracted ion chromatogram (EIC)\\u000a of m\\/z 149, free TBHQ was observed in rat serum after dosing TBHQ at 350 mg\\/kg to male and female Sprague–Dawley (SD) rats. Four\\u000a major metabolites of TBHQ

  6. Determination of Cd, Co, Cu, Fe, Mn, Ni and Zn in coral skeletons by chelation ion chromatography

    Microsoft Academic Search

    William Shotyk; Ina Immenhauser-Potthast

    1995-01-01

    Cadmium, Co, Cu, Fe, Mn, Ni and Zn incorporated in the aragonitic skeletons of corals (Porites) were analyzed by chelation ion chromatography (CIC). A 500-mg amount of bleached, oven-dried coral powder was dissolved in 1 ml of 14.4 M HNO3 and buffered at pH 5.4 ± 0.1 using 50 ml of 2 M ammonium acetate. A 30-g amount of sample

  7. Analysis of pesticides in fruits by pressurized liquid extraction and liquid chromatography–ion trap–triple stage mass spectrometry

    Microsoft Academic Search

    Cristina Blasco; Yolanda Picó

    2005-01-01

    A multi-residue method using pressurized liquid extraction (PLE) and liquid chromatography–quadrupole ion trap–triple stage mass spectrometry (LC–IT–MS3) has been developed for determining trace levels of pesticides in fruits. The selected pesticides can be distinguished in: benzimidazoles and azoles, organophosphorus, carbamates, neonicotinoids, and acaricides. PLE has been optimized to extract these pesticide residues from oranges and peaches by studying the effect

  8. An improved thin-layer chromatography\\/mass spectrometry coupling using a surface sampling probe electrospray ion trap system

    Microsoft Academic Search

    Michael J. Ford; Gary J. Van Berkel

    2004-01-01

    A combined surface sampling probe\\/electrospray emitter coupled with an ion trap mass spectrometer was used for the direct read out of unmodified reversed-phase C18 thin-layer chromatography (TLC) plates. The operation of the surface sampling electrospray ionization interface in positive and negative ionization modes was demonstrated through the direct analysis of TLC plates on which a commercial test mix comprised of

  9. Identification and dating of the fountain pen ink entries on documents by ion-pairing high-performance liquid chromatography

    Microsoft Academic Search

    Xiang-Feng Wang; Jing Yu; Meng-Xia Xie; Ya-Tong Yao; Jie Han

    2008-01-01

    A novel approach for the identification and dating of the fountain pen ink entries on paper has been established by ion-pairing high-performance liquid chromatography (IP-HPLC). Twelve black and six red fountain inks have been collected, and their ink entries have been prepared by drawing lines on paper. The chromatographic conditions for separation of their dye components after extraction with solvents

  10. Determination of Sulfur in High-Level Waste Sludge by Inductively Coupled Plasma-Atomic Emission Spectroscopy and Ion Chromatography

    SciTech Connect

    COLEMAN, CJ

    2004-04-22

    Significant differences (approximately 30 percent) have been observed in the sulfur measurements in high-level waste sludge by the Analytical Development Section (ADS) using the inductively coupled plasma-atomic emission spectroscopy (ICP-AES) method compared with the ADS ion chromatography (IC) method. Since the measured concentrations of sulfur in the sludge approached the maximum concentration that can be processed in the DWPF, experiments were performed to determine the source of the differences and assess the true accuracy of sulfur measurements.

  11. Analysis of psilocybin and psilocin in Psilocybe subcubensis GUZMÁN by ion mobility spectrometry and gas chromatography–mass spectrometry

    Microsoft Academic Search

    Thomas Keller; Andrea Schneider; Priska Regenscheit; Richard Dirnhofer; Thomas Rücker; Jürgen Jaspers; Wolfgang Kisser

    1999-01-01

    A new method has been developed for the rapid analysis of psilocybin and\\/or psilocin in fungus material using ion mobility spectrometry. Quantitative analysis was performed by gas chromatography–mass spectrometry after a simple one-step extraction involving homogenization of the dried fruit bodies of fungi in chloroform and derivatization with MSTFA. The proposed methods resulted in rapid procedures useful in analyzing psychotropic

  12. The determination of 63 Ni and 99 T c in class C waste by ion chromatography and scintillation detection

    Microsoft Academic Search

    C. D. Morgan; S. M. Frank; C. D. Monghan; A. P. Maddison

    1998-01-01

    A procedure using high performance ion chromatography coupled with on-line scintillation counting and described for the determination\\u000a of nickel-63 and technecium-99 radioisotopes in irradiated stainless steel. Commercially available chromatograph équipment,\\u000a columns and online scintillation detectors were used. The method provides detection limits for63Ni and99Tc within the range needed the determination of these radioisotopes in class “C” waste streams at our

  13. Analysis of the monoenoic fatty acid distribution in hydrogenated vegetable oils by silver-ion high-performance liquid chromatography

    Microsoft Academic Search

    R. O. Adlof; L. C. Copes; E. A. Emken

    1995-01-01

    A silver-ion high-performance liquid chromatography column (hexane\\/acetonitrile as solvent, ultraviolet detection) was used\\u000a to analyze the fatty acid distribution (as fatty acid methyl esters) of a representative sample of hydrogenated oil. Fractions\\u000a containingcis- andtrans-18:1 isomers were readily separated. The positional fatty acid isomers were separated by rechromatographing these fractions.\\u000a The elution order and percent compositions were compared with results obtained

  14. A Volatile Organic Analyzer for Space Station - Description and evaluation of a gas chromatography/ion mobility spectrometer

    NASA Technical Reports Server (NTRS)

    Limero, Thomas; Brokenshire, John; Cumming, Colin; Overton, ED; Carney, Ken; Cross, Jay; Eiceman, Gary; James, John

    1992-01-01

    An on-board Volatile Organic Analyzer (VOA), an essential component of the Environmental Health System (EHS) air-quality monitoring strategy, is described. The strategy is aimed at warning the crew and ground personnel if volatile compounds exceed safe exposure limits. The VOA uses a combination of gas chromatography (GC) and ion-mobility spectrometry (IMS) for environmental monitoring and analysis. It is concluded that the VOA dual-mode detection capability and the ion mobilities in the drift region are unique features that can assist in the resolution of coeluting GC peaks. The VOA is capable of accurately identifying and quantifying target compounds in a complex mixture.

  15. Determination of low molecular weight monocarboxylic Acid gases in the atmosphere by parallel plate diffusion scrubber-ion chromatography.

    PubMed

    Lee, Bokyoung; Hwangbo, Yown; Lee, Dong Soo

    2009-08-01

    A method has been developed for the determination of the concentration of low molecular weight monocarboxylic acid gases in the atmosphere. The method involves quantitative collection of analyte gases using a parallel plate diffusion scrubber and subsequent ion analysis by ion chromatography. Among the gases are formic acid, acetic acid, propionic acid, n-butyric acid, and n-valeric acid. Method detection limits are on the order of sub to low parts-per-trillion by volume. The method has been successfully applied to ambient air analysis. PMID:19772719

  16. Characterization of currently marketed heparin products: reversed-phase ion-pairing liquid chromatography mass spectrometry of heparin digests.

    PubMed

    Brustkern, Adam M; Buhse, Lucinda F; Nasr, Moheb; Al-Hakim, Ali; Keire, David A

    2010-12-01

    Here we report results from the analyses by enzymatic digestion and reversed-phase ion-pairing liquid chromatography mass spectrometry (RPIP-LC-MS) of active pharmaceutical ingredient (API) unfractionated heparins (UFHs) from six different manufacturers and one USP standard sample. We employed a reverse phase ion-pairing chromatography method using a C(18) column and hexylamine as the ion-pairing reagent with acetonitrile gradient elution to separate disaccharides generated from the digestion of the heparins by lyase I and III (E.C. 4.2.2.7 and 4.2.2.8) before introduction into an ion-trap mass spectrometer by an electrospray ionization (ESI) interface. Extracted ion chromatograms (EICs) were used to determine the relative abundance of the disaccharides by mass spectrometry. Eight disaccharides were observed and a similar composition profile was observed from digests of 20 UFH samples. The compositional profile determined from these experiments provides a measure of the norm and range of variation in "good" heparin to which future preparations can be compared. Furthermore, the profile obtained in the RPIP-LC-MS assay is sensitive to the presence of the contaminant, oversulfated chondroitin sulfate A (OSCS), in heparin. PMID:21069966

  17. Simultaneous determination of nucleosides and nucleotides in dietary foods and beverages using ion-pairing liquid chromatography–electrospray ionization-mass spectrometry

    Microsoft Academic Search

    Noriko Yamaoka; Yuko Kudo; Katsunori Inazawa; Satoko Inagawa; Makoto Yasuda; Ken-ichi Mawatari; Kazuya Nakagomi; Kiyoko Kaneko

    2010-01-01

    A method using ion-pairing liquid chromatography–electrospray ionization (ESI)-mass spectrometry (MS) was developed for the simultaneous determination of 23 types of purine or pyrimidine nucleosides and nucleotides in dietary foods and beverages. Dihexylammonium acetate (DHAA) was used as an ion-pairing agent and an ultra performance liquid chromatography (UPLC™) system with a reversed-phase column and a gradient program was employed for the

  18. A study of the analytical behaviour of selected synthetic and naturally occurring coumarins using liquid chromatography, ion trap mass spectrometry, gas chromatography and polarography and the construction of an appropriate database for coumarin characterisation

    Microsoft Academic Search

    W. Franklin Smyth; Venkataraman N. Ramachandran; Catherine J. Hack; Clare Joyce; Edmund O’Kane

    2006-01-01

    The aim of this paper is to provide analytical chemical information on a range of naturally occurring and synthetic coumarins. This analytical chemical information on liquid chromatography–electrospray ionisation-mass spectrometry (HPLC–ESI-MS), ion trap mass spectrometry (ESI-MSn), gas chromatography-flame ionisation detection (GLC-FID) and polarographic behaviour is then incorporated into a database which is of use in identifying unknown coumarins isolated from natural

  19. Multiple-stage mass spectrometric analysis of six pesticides in oranges by liquid chromatography–atmospheric pressure chemical ionization–ion trap mass spectrometry

    Microsoft Academic Search

    Cristina Blasco; Yolanda Picó

    2004-01-01

    Six pesticides were determined by liquid chromatography (LC) with positive ion (PI) atmospheric pressure chemical ionization quadrupole ion-trap tandem mass spectrometry (APCI–MS–MS). Ion fragmentation was studied by MS, MS2 and MS3. Fragmentation of the pesticides produced ions formed by various losses from the side-chains and through heterocyclic ring opening, but without any common fragmentation pathway. Multiple reaction monitoring (MRM) of

  20. Ion trace detection algorithm to extract pure ion chromatograms to improve untargeted peak detection quality for liquid chromatography/time-of-flight mass spectrometry-based metabolomics data.

    PubMed

    Wang, San-Yuan; Kuo, Ching-Hua; Tseng, Yufeng J

    2015-03-01

    Able to detect known and unknown metabolites, untargeted metabolomics has shown great potential in identifying novel biomarkers. However, elucidating all possible liquid chromatography/time-of-flight mass spectrometry (LC/TOF-MS) ion signals in a complex biological sample remains challenging since many ions are not the products of metabolites. Methods of reducing ions not related to metabolites or simply directly detecting metabolite related (pure) ions are important. In this work, we describe PITracer, a novel algorithm that accurately detects the pure ions of a LC/TOF-MS profile to extract pure ion chromatograms and detect chromatographic peaks. PITracer estimates the relative mass difference tolerance of ions and calibrates the mass over charge (m/z) values for peak detection algorithms with an additional option to further mass correction with respect to a user-specified metabolite. PITracer was evaluated using two data sets containing 373 human metabolite standards, including 5 saturated standards considered to be split peaks resultant from huge m/z fluctuation, and 12 urine samples spiked with 50 forensic drugs of varying concentrations. Analysis of these data sets show that PITracer correctly outperformed existing state-of-art algorithm and extracted the pure ion chromatograms of the 5 saturated standards without generating split peaks and detected the forensic drugs with high recall, precision, and F-score and small mass error. PMID:25622715

  1. Isoelectric point separation of proteins by capillary pH-gradient ion-exchange chromatography.

    PubMed

    Andersen, Thomas; Pepaj, Milaim; Trones, Roger; Lundanes, Elsa; Greibrokk, Tyge

    2004-02-01

    In the present work, isoelectric point (pl) separation of proteins by pH-gradient ion-exchange chromatography (IEC) on packed capillary columns is demonstrated. The development of a miniaturized flow-through pH probe for reliable pH monitoring of the column effluent, which was an important technical challenge for adapting this technique to capillary dimensions, was solved by designing a low microliter per minute flow rate housing to a commercially available micro pH probe. Highly linear outlet pH-gradients within the pH range 8.5-4.0 were obtained when applying simple inexpensive buffers consisting solely of piperazine, N-methylpiperazine and imidazole on 10 cm x 0.32 mm i.d. fused silica capillaries packed with anion-exchange poly(styrene divinylbenzene)-based macroporous materials, i.e. 10 microm Mono P from Amersham Biosciences and 10 microm PL-SAX from PolymerLabs. Furthermore, when using a pH-gradient from 6.8 to 4.3, both columns were able to baseline separate the A and B genetic variants of beta-lactoglobulin, which differ with two amino acid residues only, but the PL-SAX column provided almost a two-fold decrease in peak widths compared to the Mono P column. The influence of varying the buffer concentration, injection volume and column temperature on the peak widths and resolution of the beta-lactoglobulins was investigated, e.g. a 100 microl sample of dilute beta-lactoglobulins was injected directly on the column with practically no increase in peak width as compared to what obtained with conventional injection volumes. Finally, a pH-gradient from 6.8 to 4.3 was used to separate proteins in skimmed bovine milk on the PL-SAX column. The milk was simply diluted 1:10 (v/v) with water and filtrated before injection. PMID:14763806

  2. [Analysis of piperidinium ionic liquid cations by ion chromatography with direct conductivity detection].

    PubMed

    Zhang, Renqing; Yu, Hong; Liu, Yuzhen

    2012-07-01

    A method of ion chromatography with direct conductivity detection was established to determine three piperidinium ionic liquid cations, i. e. N-methyl, ethyl piperidinium cation ([MEPi]+), N-methyl, propyl piperidinium cation ([MPPi]+) and N-methyl, butyl piperidinium cation ([MBPi]+). The effects of eluent types, eluent concentration and column temperature on the retention of the cations were investigated with sulfonic acid base cation exchange column using ethylenediamine-citric acid-acetonitrile as eluent. The results indicated that, with the increase of column temperature, the retention times of piperidinium cations were reduced, so the retention process of piperidinium cations was exothermic. The retentions of piperidinium cation homologue accorded with carbon number rule. The successful separation of the three piperidinium cations within 7 min was achieved using the optimized eluent of 0.2 mmol/L ethylenediamine-0.3 mmol/L citric acid-3% acetonitrile (pH 4.4) at a flow rate of 1.0 mL/min and the column temperature of 30 degrees C. Under these conditions, the detection limits at a signal-to-noise ratio of 3 for [MEPi]+, [MPPi] and [MBPi]+ were 0.14, 0.20 and 0.56 mg/L, respec-tively. The relative standard deviations (n = 5) for peak areas were less than 1.2%. The method has been applied to the determination of piperidinium ionic liquids synthesized in chemical laboratory with the spiked recoveries of 97.6% to 105.1%. The method is accurate, reliable, rapid, and has better practicability. PMID:23189670

  3. Method for the determination of ammonium in cigarette tobacco using ion chromatography.

    PubMed

    Watson, Christina Vaughan; Valentin-Blasini, Liza; Damian, Maria; Watson, Clifford H

    2015-07-01

    Ammonia and other alkaline substances have been postulated to be important in cigarette design. The most significant potential contribution of ammonia is a possible interaction with the native, protonated nicotine in the smoke. Ammonia is more alkaline than nicotine and could facilitate a shift in the acid/base equilibrium where a fraction of the total nicotine converts to the more lipophilic, non-protonated form. This non-protonated, or free-base, form of nicotine absorbs more efficiently across membranes, resulting in more rapid delivery to the smoker's bloodstream. Ammonia and other potential ammonia sources, such as additives like diammonium phosphate, could influence the acid-base dynamics in cigarette smoke and ultimately the rate of nicotine delivery. To examine and characterize the ammonia content in modern cigarettes, we developed a fast, simple and reliable ion chromatography based method to measure extractable ammonia levels in cigarette filler. This approach has minimal sample preparation and short run times to achieve high sample throughput. We quantified ammonia levels in tobacco filler from 34 non-mentholated cigarette brands from 3 manufacturers to examine the ranges found across a convenience sampling of popular, commercially available domestic brands and present figures of analytical merit here. Ammonia levels ranged from approximately 0.9 to 2.4mg per gram of cigarette filler between brands and statistically significance differences were observed between brands and manufacturers. Our findings suggest that ammonia levels vary by brand and manufacturer; thus in domestic cigarettes ammonia could be considered a significant design feature because of the potential influence on smoke chemistry. PMID:25934256

  4. Determination of vanillin, ethyl vanillin, and coumarin in infant formula by liquid chromatography-quadrupole linear ion trap mass spectrometry.

    PubMed

    Shen, Yan; Han, Chao; Liu, Bin; Lin, Zhengfeng; Zhou, Xiujin; Wang, Chengjun; Zhu, Zhenou

    2014-02-01

    A simple, precise, accurate, and validated liquid chromatography-quadrupole linear ion trap mass spectrometry method was developed for the determination of vanillin, ethyl vanillin, and coumarin in infant formula samples. Following ultrasonic extraction with methanol/water (1:1, vol/vol), and clean-up on an HLB solid-phase extraction cartridge (Waters Corp., Milford, MA), samples were separated on a Waters XSelect HSS T3 column (150 × 2.1-mm i.d., 5-?m film thickness; Waters Corp.), with 0.1% formic acid solution-acetonitrile as mobile phase at a flow rate of 0.25 mL/min. Quanti?cation of the target was performed by the internal standard approach, using isotopically labeled compounds for each chemical group, to correct matrix effects. Data acquisition was carried out in multiple reaction monitoring transitions mode, monitoring 2 multiple reaction monitoring transitions to ensure an accurate identi?cation of target compounds in the samples. Additional identi?cation and con?rmation of target compounds were performed using the enhanced product ion modus of the linear ion trap. The novel liquid chromatography-quadrupole linear ion trap mass spectrometry platform offers the best sensitivity and speci?city for characterization and quantitative determination of vanillin, ethyl vanillin, and coumarin in infant formula and fulfills the quality criteria for routine laboratory application. PMID:24359823

  5. Quantitative LC-MS of polymers: determining accurate molecular weight distributions by combined size exclusion chromatography and electrospray mass spectrometry with maximum entropy data processing.

    PubMed

    Gruendling, Till; Guilhaus, Michael; Barner-Kowollik, Christopher

    2008-09-15

    We report on the successful application of size exclusion chromatography (SEC) combined with electrospray ionization mass spectrometry (ESI-MS) and refractive index (RI) detection for the determination of accurate molecular weight distributions of synthetic polymers, corrected for chromatographic band broadening. The presented method makes use of the ability of ESI-MS to accurately depict the peak profiles and retention volumes of individual oligomers eluting from the SEC column, whereas quantitative information on the absolute concentration of oligomers is obtained from the RI-detector only. A sophisticated computational algorithm based on the maximum entropy principle is used to process the data gained by both detectors, yielding an accurate molecular weight distribution, corrected for chromatographic band broadening. Poly(methyl methacrylate) standards with molecular weights up to 10 kDa serve as model compounds. Molecular weight distributions (MWDs) obtained by the maximum entropy procedure are compared to MWDs, which were calculated by a conventional calibration of the SEC-retention time axis with peak retention data obtained from the mass spectrometer. Comparison showed that for the employed chromatographic system, distributions below 7 kDa were only weakly influenced by chromatographic band broadening. However, the maximum entropy algorithm could successfully correct the MWD of a 10 kDa standard for band broadening effects. Molecular weight averages were between 5 and 14% lower than the manufacturer stated data obtained by classical means of calibration. The presented method demonstrates a consistent approach for analyzing data obtained by coupling mass spectrometric detectors and concentration sensitive detectors to polymer liquid chromatography. PMID:18690749

  6. A size exclusion-reversed phase two dimensional-liquid chromatography methodology for stability and small molecule related species in antibody drug conjugates.

    PubMed

    Li, Yi; Gu, Christine; Gruenhagen, Jason; Zhang, Kelly; Yehl, Peter; Chetwyn, Nik P; Medley, Colin D

    2015-05-01

    Antibody drug conjugates (ADCs) are complex therapeutic agents combining the specific targeting properties of antibodies and highly potent cytotoxic small molecule drugs to selectively eliminate tumor cells while limiting the toxicity to normal healthy tissues. One unique critical quality attribute of ADCs is the content of unconjugated small molecule drug present from either incomplete conjugation or degradation of the ADC. In this work, size exclusion chromatography (SEC) was coupled with reversed-phase (RP) HPLC in an online 2-dimensional chromatography format for identification and quantitation of unconjugated small molecule drugs and related small molecule impurities in ADC samples directly without sample preparation. The SEC method in the 1st dimension not only separated the small molecule impurities from the intact ADC, but also provided information about the size variants (monomer, dimer, aggregates, etc.) of the ADC. The small molecule peak from the SEC was trapped and sent to a RP-HPLC in the 2nd dimension to further separate and quantify the different small molecule impurities present in the ADC sample. This SEC-RP 2D-LC method demonstrated excellent precision (%RSD<2.0), linearity (r(2)=0.9999), sensitivity (LOQ of 0.05?g/mL of free drug in ADC sample) and accuracy (95-105% recovery of spiked samples). The 2D-LC method was further utilized to study the stability of an ADC drug product at different temperatures and pHs. Both small molecule degradation products and aggregation of the conjugate were observed in the stability samples and the degradation pathways of the ADC were investigated. This 2D-LC method offers a powerful tool for ADC characterization and provides valuable information for conjugation and formulation development. PMID:25818558

  7. [Isolation of expressed in E. coli human interferon beta1b (Ser17) by ion-exchange chromatography].

    PubMed

    Romanov, V P; Bezuglov, V V; Bobrov, M Iu; Kostromina, T I; Feofanov, S A; Miroshnikov, A I

    2011-01-01

    A method for isolation of interferon beta1b (Serl7) from inclusion bodies, comprising the steps of solution and reduction of protein from the inclusion bodies, refolding, chromatography on DEAE-Sepharose, chromatography on SP-Sepharose, concentrating, desalting and addition of stabilizers. The solution of reduced protein was diluted with pH 8.0 buffer of 50 mM Tris-HCl, 25 microM CuCl2 and 0.5% Twin 20 for refolding. We used gradient of pH (from 9.3 upto 11.3) for elution of interferon-beta from cation-exchange column. We concentrated of eluate and then desalted on the Sephadex G-50 column with 1 mM NaOH. Then the protein solution was neutralized with mannitol and Na-phosphate. Obtained preparation of interferon-beta was pure by gel-electrophoresis and by HPLC analysis, and had practically indentical level of antiproliferative activity with well-known preparation of Betaferone. Thus we show the possibility of isolation and obtaining of pure and active interferone-beta by ion-exchange chromatography in the presence of non-ion detergent Twin 20. We believe this method for interferon betalb preparation is perspective for scaling and using in the develop of industrial technology for production of this preparation. PMID:21899047

  8. Separation and quantitation of monovalent anionic and cationic species in mainstream cigarette smoke aerosols by high-performance ion chromatography.

    PubMed

    Nanni, E J; Lovette, M E; Hicks, R D; Fowler, K W; Borgerding, M F

    1990-08-01

    A simple method has been developed to separate and quantitate monovalent ionic species in mainstream cigarette smoke aerosols based on ion chromatography (IC) with conductivity detection. The method entails collecting the smoke aerosol particulate phase by electrostatic precipitation, dissolving the smoke condensate in methanol (MeOH), and separating the ionic species on either a cation- or anion-exchange column. The method has been applied to the analysis of smoke aerosols from two cigarettes, 1R4F Kentucky Reference cigarettes and a new cigarette that heats but does not burn tobacco. The predominant cations in smoke aerosols from 1R4F Kentucky Reference and the new cigarettes are sodium (Na+), ammonium (NH4+), and potassium (K+) ions; the predominant anions are acetate (AcO-) and formate (HCOO-). Trace amounts of chloride (Cl-), nitrite (NO2-), and nitrate (NO3-) ions are also present. PMID:2229270

  9. Characterization of a protein conjugate using an asymmetrical-flow field-flow fractionation and a size-exclusion chromatography with multi-detection system.

    PubMed

    Rebolj, Katja; Pahovnik, David; Zagar, Ema

    2012-09-01

    In this study we present detailed characterization of a protein-PEG conjugate using two separation techniques, that is, asymmetrical-flow field-flow fractionation (AF4) and size-exclusion chromatography (SEC), which were online coupled to a series of successively connected detectors: an ultraviolet, a multiangle light-scattering, a quasi-elastic light-scattering, and a refractive-index detector (UV-MALS(QELS)-RI). Matrix-assisted laser-desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) was used as a complementary characterization technique. The results of AF4 as well as SEC on two columns connected in series, with both separation techniques coupled to a multidetection system, indicate the uniform molar mass and chemical composition of the conjugate, that is, the molar ratio of protein to PEG is 1/1, the presence of minute amounts of residual unreacted protein and the aggregates with the same chemical composition as that of the conjugate. Since the portion of aggregated species is smaller in the acetate buffer solution containing 5% sorbitol than in the acetate buffer solution with 200-mM sodium chloride, the former buffer solution is more suitable for conjugate storage. The separation using only one SEC column results in poorly resolved peaks of the PEGylated protein conjugate and the aggregates, whereas MALDI-TOF MS analysis reveal the presence of the residual protein, but not the aggregates. PMID:22876760

  10. Study of pH effects on the evolution of properties of brown-water natural organic matter as revealed by size-exclusion chromatography during photocatalytic degradation.

    PubMed

    Valencia, Sergio; Marín, Juan; Velásquez, Jorge; Restrepo, Gloria; Frimmel, Fritz H

    2012-03-15

    This study shows the effect of pH on the photocatalytic degradation of natural organic matter (NOM). The experiments were carried out in batch reactor (a solar UV-light simulator) with Degussa P-25 titanium dioxide (TiO2). The NOM degradation was followed by size-exclusion chromatography for dissolved organic carbon (DOC), ultraviolet absorption and fluorescence-detection (SEC-DOC, SEC-UV254 and SEC-Fl254/450). Changes in pH values affected the adsorption of NOM onto TiO2, but did not affect the photodegradation sequence of NOM. For high or low pH values, the degradation of the NOM preferentially removed the larger molecular size fraction in comparison to the middle and small molecular size fractions, resulting in the relative increase of these smaller fractions. This sequence of NOM degradation leads to the evolution of the formation potential for disinfection by-products (DBPs). Specifically, the trihalomethanes and halogenated organic compounds formation potential (THMF and AOXFP) decreased steadily. PMID:22209274

  11. Evaluations of the TiO2/simulated solar UV degradations of XAD fractions of natural organic matter from a bog lake using size-exclusion chromatography.

    PubMed

    Valencia, Sergio; Marín, Juan M; Restrepo, Gloria; Frimmel, Fritz H

    2013-09-15

    This work reports on the changes in compositions of humic acids (HAs) and fulvic acids (FAs) during photocatalytic degradation. The HAs and FAs were obtained from the XAD-resin fractionation of natural-organic matter (NOM) from a bog lake (Lake Hohloh, Black Forest, Germany). Degussa P-25 titanium dioxide (TiO2) in a suspension and a solar UV simulator (batch reactor) were used in the experiments. The photocatalytic degradation of the HAs and FAs were monitored using size-exclusion chromatography (SEC) equipped with dissolved organic carbon (DOC) and ultraviolet (UV254) detection (SEC-DOC and SEC-UV254) and UV-Vis spectrophotometry. The evolutions of the photocatalytic degradations of the HA and FA fractions were selective. The photocatalytic degradation started with the degradations of high molecular weight compounds with relatively high UV254 absorbances in the HA and FA fractions to yield low molecular weight compounds showing less specific UV254 absorbances. Observance of the same tendency for the original NOM from Lake Hohloh indicates that these XAD-fractions still having complex compound mixtures. However, the larger molecular weight fractions of the FAs showed higher preferential adsorptions onto TiO2, which caused their faster degradation rates. Furthermore, FAs showed a greater reduction of the total THM formation potential (TTHMFP) and the organic halogen compounds adsorbable on activated carbon formation potential (AOXFP), in comparison with the HAs. PMID:23863374

  12. Estimation of band broadening in size-exclusion chromatography. I. A method based on analyzing narrow standards with a molar mass-sensitive detector.

    PubMed

    Yossen, Mariana M; Vega, Jorge R; Meira, Gregorio R

    2006-09-22

    A method is proposed for estimating the (asymmetrical and non-uniform) band broadening function (BBF) in size-exclusion chromatography (SEC). The following data are required: the molar mass calibration and the concentration- and molar mass chromatograms of a set of narrow standards. In the narrow range of each standard, the BBF is uniform but skewed. Each uniform BBF is estimated through a nonlinear optimization procedure that compares one (of the two) measured chromatograms with its theoretical prediction based on the other chromatogram. The method is validated with numerical examples that simulate the analyses of narrow standards exhibiting log-normal and Poisson weight chain length distributions. The BBF can be assumed of arbitrary shape, or represented by an exponentially-modified Gaussian (EMG). From the uniform BBF estimate, the true polydispersity of the standard can be determined. The global non-uniform BBF is obtained by interpolation between a set of uniform BBFs covering a wide range of elution volumes. PMID:16828786

  13. Size exclusion and reversed-phase high-performance liquid chromatography/UV for routine control of thermal processing of cows' and donkey milk major proteins.

    PubMed

    Pinho, Carina; Martins, Zita E; Petisca, Catarina; Figurska, Agata M; Pinho, Olívia; Ferreira, Isabel M P L V O

    2012-05-01

    Cows' and donkey milks (raw and thermally processed) and respective whey were analysed for quantification of major proteins. Two different chromatographic approaches, size exclusion (SE-HPLC) and reversed-phase high performance liquid chromatography (RP-HPLC) both coupled to UV detection were used. Usefulness of these methods for routine control of the effect of thermal processing was evaluated. The external standard method was used to calibrate the SE-HPLC and RP-HPLC systems. Concerning quantification of ?-lactoglobulin (?-lg), ?-lactalbumin (?-la), lysozyme (lys), and total casein (cn), no significant differences between results obtained by SE-HPLC and by RP-HPLC (t-test, P>0·05) were observed for raw milks and whey. Heating of cows' milk promoted aggregation of denatured proteins as observed by SE-HPLC, whereas ?-la and ?-lg from donkey milk were stable to thermal processing at 100 °C (5 min). Lys was quantified in donkey raw milk and whey however, in thermally processed donkey milk lys was denatured and could not be quantified by HPLC. PMID:22420770

  14. Size-exclusion chromatography-mass spectrometry with m-nitrobenzyl alcohol as post-column additive for direct characterization of size variants of monoclonal antibodies.

    PubMed

    Xu, Chong-Feng; Zang, Li; Weiskopf, Andrew

    2014-06-01

    Size-exclusion chromatography (SEC) is commonly used to monitor low molecular weight fragments and aggregates present in recombinant monoclonal antibody (mAb) biopharmaceuticals. It has been previously demonstrated that SEC could be coupled with mass spectrometry (MS) to directly measure the molecular weights of these protein species to aid in their identification. However, the use of certain mobile phase modifiers led to compromised sensitivity in MS detection. In this work, we demonstrate that the use of m-nitrobenzyl alcohol (m-NBA) as a post-column additive in an SEC-MS method is able to improve the ionization of antibody light chain and heavy chain approximately 7-fold and 2-fold, respectively, and thus allows the MS detection of low-abundance size variants present in mAb biopharmaceuticals. Application of the 15-min reducing SEC-UV/MS method enabled the direct identification of size variants present in an IgG1 mAb sample. One high molecular weight species observed under reducing conditions was identified to be a thioether-linked heterodimer of light chain and heavy chain. Multiple lower molecular weight species were found to result from cleavage of the heavy chain at a number of sites throughout the conserved sequence. The reducing SEC-UV/MS method provides a straightforward approach for identification of size variants present in mAb and may be applicable generally to all types of mAb biopharmaceuticals. PMID:24835510

  15. Impact of protein concentration on the determination of thiolic groups of ovalbumin: a size exclusion chromatography-chemical vapor generation-atomic fluorescence spectrometry study via mercury labeling.

    PubMed

    Campanella, Beatrice; Onor, Massimo; D'Ulivo, Alessandro; Giannarelli, Stefania; Bramanti, Emilia

    2014-02-18

    We optimized a hyphenated system based on size exclusion chromatography coupled to a microwave/UV mercury oxidation system and an atomic fluorescence detector (SEC-CVG-AFS) for the online oxidation of free and protein-complexed p-hydroxymercuribenzoic acid (pHMB) without the employment of chemical oxidizing agents. This system has been applied to the study of labeling of thiolic groups of native ovalbumin (OVA) as a function of protein concentration. We found that the protein concentration strongly affects the species distribution of OVA, the number of thiolic groups titrated in each species, and thus, the accuracy in the determination of the total number of thiolic groups. The amount of titrated sulfhydryl groups in the protein concentration range investigated (5-100 ?mol L(-1)) varied from 2.40 ± 0.01 to 1.85 ± 0.05 for the monomeric form of OVA and from 4.63 ± 0.01 to 5.63 ± 0.05 for the total OVA, which represents more than four theoretical number of reduced Cys. This information is important from the analytical point of view because it suggests that, unless to operate with diluted concentration of protein, the number of titrated thiolic groups results from both the aspecific interaction of the probe with aggregates species and to the specific bond of the probe with the accessible -SH groups. PMID:24502672

  16. Absolute molecular weight determination of hypromellose acetate succinate by size exclusion chromatography: use of a multi angle laser light scattering detector and a mixed solvent.

    PubMed

    Chen, Raymond; Ilasi, Nicholas; Sekulic, Sonja S

    2011-12-01

    Molecular weight distribution is an important quality attribute for hypromellose acetate succinate (HPMCAS), a pharmaceutical excipient used in spray-dried dispersions. Our previous study showed that neither relative nor universal calibration method of size exclusion chromatography (SEC) works for HPMCAS polymers. We here report our effort to develop a SEC method using a mass sensitive multi angle laser light scattering detector (MALLS) to determine molecular weight distributions of HPMCAS polymers. A solvent screen study reveals that a mixed solvent (60:40%, v/v 50mM NaH(2)PO(4) with 0.1M NaNO(3) buffer: acetonitrile, pH* 8.0) is the best for HPMCAS-LF and MF sub-classes. Use of a mixed solvent creates a challenging condition for the method that uses refractive index detector. Therefore, we thoroughly evaluated the method performance and robustness. The mean weight average molecular weight of a polyethylene oxide standard has a 95% confidence interval of (28,443-28,793) g/mol vs. 28,700g/mol from the Certificate of Analysis. The relative standard deviations of average molecular weights for all polymers are 3-6%. These results and the Design of Experiments study demonstrate that the method is accurate and robust. PMID:21840663

  17. Antibiotics as low-molecular-mass displacers in ion-exchange displacement chromatography

    Microsoft Academic Search

    Amitava Kundu; Suresh Vunnum; Steven M. Cramer

    1995-01-01

    While the ability to carry out simultaneous concentration and purification in a single displacement step has significant advantages for downstream processing of pharmaceuticals, a major impediment to the implementtion of displacement chromatography has been the lack of suitable displacer compounds. An important recent advance in the state-of-the-art of displacement chromatography has been the discovery that low-molecular-mass dendritic polymers and protected

  18. An Ultra-Trace Analysis Technique for SF6 Using Gas Chromatography with Negative Ion Chemical Ionization Mass Spectrometry.

    PubMed

    Jong, Edmund C; Macek, Paul V; Perera, Inoka E; Luxbacher, Kray D; McNair, Harold M

    2015-07-01

    Sulfur hexafluoride (SF6) is widely used as a tracer gas because of its detectability at low concentrations. This attribute of SF6 allows the quantification of both small-scale flows, such as leakage, and large-scale flows, such as atmospheric currents. SF6's high detection sensitivity also facilitates greater usage efficiency and lower operating cost for tracer deployments by reducing quantity requirements. The detectability of SF6 is produced by its high molecular electronegativity. This property provides a high potential for negative ion formation through electron capture thus naturally translating to selective detection using negative ion chemical ionization mass spectrometry (NCI-MS). This paper investigates the potential of using gas chromatography (GC) with NCI-MS for the detection of SF6. The experimental parameters for an ultra-trace SF6 detection method utilizing minimal customizations of the analytical instrument are detailed. A method for the detection of parts per trillion (ppt) level concentrations of SF6 for the purpose of underground ventilation tracer gas analysis was successfully developed in this study. The method utilized a Shimadzu gas chromatography with negative ion chemical ionization mass spectrometry system equipped with an Agilent J&W HP-porous layer open tubular column coated with an alumina oxide (Al2O3) S column. The method detection limit (MDL) analysis as defined by the Environmental Protection Agency of the tracer data showed the method MDL to be 5.2 ppt. PMID:25452581

  19. Determination of thorium and light rare-earth elements in soil water and its high molecular mass organic fractions by inductively coupled plasma mass spectrometry and on-line-coupled size-exclusion chromatography

    Microsoft Academic Search

    Evelton A. Casartelli; Norbert Miekeley

    2003-01-01

    Inductively coupled plasma mass spectrometry (ICP–MS) has been used for the determination of thorium and light rare-earth elements (LREEs) in soil and soil water samples from a mineral deposit (Morro do Ferro, Minas Gerais, Brazil). Size-exclusion chromatography (SEC) on-line coupled to ICP–MS and UV-detection was applied to verify possible association\\/complexation of these elements with organic matter in soil water separated

  20. Organic analysis by ion chromatography. 1. Determination of aromatic amines and aromatic diisocyanates by cation-exchange chromatography with amperometric detection.

    PubMed

    Zhu, Yan; Wang, Muhua; Du, Huangyong; Wang, Fang; Mou, Shifen; Haddad, Paul R

    2002-05-17

    A method has been developed for the simultaneous determination of a range of aromatic amines using cation-exchange chromatography performed on a standard ion chromatography column using d.c. amperometric detection. The analytes separated were 2,4- and 2,6-toluenediamine (2,4- and 2,6-TDA), aniline, o-toluidine, benzidine, p-chloroaniline, 4,4'-diaminodiphenyl (4,4'-DDP), m-nitroaniline and 1-naphthylamine. A Dionex CS12 column was used with gradient elution from an initial eluent of 5% CH3CN+35 mM H2SO4 to 27% CH3CN+35 mM H2SO4 (at 35 min). Detection limits in the range 2.6-22.6 microg/l were observed for all analytes except m-nitroaniline, for which the detection limit was 201 microg/l. Linear calibrations and good precision were observed and the method was applied to the determination of benzidine, p-chloroaniline and 1-naphthylamine in wastewater samples. Further, the separation was also used (after some modification of the eluent conditions) for the determination of 2,4- and 2,6-toluene diisocyanate (2,4- and 2,6-TDI) and 4,4'-methylenediphenyl diisocyanate (4,4'-MDI) after their hydrolysis to 2,4-TDA, 2,6-TDA and 4,4'-DDP. Detection limits for 2,6- and 2,4-TDI and 4,4'-MDI were 3.8, 8.2, and 11.2 microg/l, respectively. The method was applied to the determination of diisocyanates in air. PMID:12108653

  1. The evaluation of novel microwave-induced plasma sources and the inductively-coupled plasma for element specific detection for capillary supercritical fluid chromatography and ion chromatography

    SciTech Connect

    Forbes, K.A.

    1989-01-01

    This dissertation involved two aspects of the development of plasma atomic emission detectors for chromatography. Four novel microwave cavities/devices were investigated to establish the positive features and limitations of each. The enhanced Beenakker cavity (EBC) was determined to be easiest to operate and tune. An annular helium plasma was produced in a concentric torch in the EBC, and 5 ppm phosphorus was detected in aqueous solutions introduced into the 85 W plasma by means of an ultrasonic nebulizer/desolvator. The annular plasma produces more efficient analyte excitation than a filament type of plasma, and had minimal contact with the torch walls, resulting in much lower silicon emission. Gaseous and supercritical fluid carbon dioxide were introduced into the helium plasmas in the EBC and the stripline cavity. The molecular background increased significantly due to CO and CO{sup +} systems, however, the increase in C{sub 2} molecular bands was not significant. A large analytically useful window exists in the background spectrum of the plasmas in the EBC and SLC with CO{sub 2} added from a capillary supercritical fluid chromatograph (SFC). The inductively coupled plasma (ICP) was interfaced to a capillary SFC. The argon plasma was optimized for Si(I) 251.6 nm emission to detect separated organosilicon compounds selectively. The linear dynamic concentration range for octamethylcyclotetra-siloxane was 10{sup 2}, with a detection limit of 5.8 ng Si injected. The relative standard deviations of the peak heights for repetitive injections were typically 1-5%. The effects of the CO{sub 2} pressure on the plasma stability and sensitivity, and upon the spectral background are presented. An ICP was also used as an element specific detector for ion chromatography. An analytical method is presented for the determination of Didronel (1-hydroxyethylidene-l,l-disodium diphosphonate, HEDP), in standard solutions and tablet dosage formulations.

  2. Fast gas chromatography and negative-ion chemical ionization tandem mass spectrometry for forensic analysis of cannabinoids in whole blood

    Microsoft Academic Search

    Aurélien Thomas; Christèle Widmer; Gérard Hopfgartner; Christian Staub

    2007-01-01

    The present work describes a fast gas chromatography\\/negative-ion chemical ionization tandem mass spectrometric assay (Fast GC\\/NICI-MS\\/MS) for analysis of tetrahydrocannabinol (THC), 11-hydroxy-tetrahydrocannabinol (THC-OH) and 11-nor-9-carboxy-tetrahydrocannabinol (THC-COOH) in whole blood. The cannabinoids were extracted from 500?L of whole blood by a simple liquid–liquid extraction (LLE) and then derivatized by using trifluoroacetic anhydride (TFAA) and hexafluoro-2-propanol (HFIP) as fluorinated agents. Mass spectrometric

  3. Strong ion-exchange centrifugal partition chromatography as an efficient method for the large-scale purification of glucosinolates

    Microsoft Academic Search

    Alix Toribio; Jean-Marc Nuzillard; Jean-Hugues Renault

    2007-01-01

    The glucosinolates sinalbin and glucoraphanin were purified by strong ion-exchange displacement centrifugal partition chromatography (SIXCPC). The optimized conditions involved the biphasic solvent system ethyl acetate\\/n-butanol\\/water (3:2:5, v\\/v), the lipophilic anion-exchanger Aliquat 336 (trioctylmethylammonium chloride, 160 and 408mM) and a sodium iodide solution (80 and 272mM) as displacer. Amounts as high as 2.4g of sinalbin and 2.6g of glucoraphanin were obtained

  4. Characterizing string-of-pearls colloidal silica by multidetector hydrodynamic chromatography and comparison to multidetector size-exclusion chromatography, off-line multiangle static light scattering, and transmission electron microscopy.

    PubMed

    Brewer, Amandaa K; Striegel, André M

    2011-04-15

    The string-of-pearls-type morphology is ubiquitous, manifesting itself variously in proteins, vesicles, bacteria, synthetic polymers, and biopolymers. Characterizing the size and shape of analytes with such morphology, however, presents a challenge, due chiefly to the ease with which the "strings" can be broken during chromatographic analysis or to the paucity of information obtained from the benchmark microscopy and off-line light scattering methods. Here, we address this challenge with multidetector hydrodynamic chromatography (HDC), which has the ability to determine, simultaneously, the size, shape, and compactness and their distributions of string-of-pearls samples. We present the quadruple-detector HDC analysis of colloidal string-of-pearls silica, employing static multiangle and quasielastic light scattering, differential viscometry, and differential refractometry as detection methods. The multidetector approach shows a sample that is broadly polydisperse in both molar mass and size, with strings ranging from two to five particles, but which also contains a high concentration of single, unattached "pearls". Synergistic combination of the various size parameters obtained from the multiplicity of detectors employed shows that the strings with higher degrees of polymerization have a shape similar to the theory-predicted shape of a Gaussian random coil chain of nonoverlapping beads, while the strings with lower degrees of polymerization have a prolate ellipsoidal shape. The HDC technique is contrasted experimentally with multidetector size-exclusion chromatography, where, even under extremely gentle conditions, the strings still degraded during analysis. Such degradation is shown to be absent in HDC, as evidenced by the fact that the molar mass and radius of gyration obtained by HDC with multiangle static light scattering detection (HDC/MALS) compare quite favorably to those determined by off-line MALS analysis under otherwise identical conditions. The multidetector HDC results were also comparable to those obtained by transmission electron microscopy (TEM). Unlike off-line MALS or TEM, however, multidetector HDC is able to provide complete particle analysis based on the molar mass, size, shape, and compactness and their distributions for the entire sample population in less than 20 min. PMID:21428298

  5. An improved thin-layer chromatography/mass spectrometry coupling using a surface sampling probe electrospray ion trap system

    SciTech Connect

    Ford, Michael J [ORNL; Van Berkel, Gary J [ORNL

    2004-01-01

    A combined surface sampling probe/electrospray emitter coupled with an ion trap mass spectrometer was used for the direct read out of unmodified reversed-phase C18 thin-layer chromatography (TLC) plates. The operation of the surface sampling electrospray ionization interface in positive and negative ionization modes was demonstrated through the direct analysis of TLC plates on which a commercial test mix comprised of four dye compounds viz., rhodamine B, fluorescein, naphthol blue black, and fast green FCF, and an extract of the caffeine-containing plant Ilex vomitoria, were spotted and developed. Acquisition of full-scan mass spectra and automated collection of MS/MS product ion spectra while scanning a development lane along the surface of a TLC plate demonstrated the advantages of using an ion trap in this combination. Details of the sampling system, benefits of analyzing a developed lane in both positive ion and negative ion modes, levels of detection while surface scanning, surface scan speed effects, and the utility of three-dimensional data display, are also discussed.

  6. Purification of recombinant virus-like particles of porcine circovirus type 2 capsid protein using ion-exchange monolith chromatography.

    PubMed

    Zaveckas, Mindaugas; Snipaitis, Simas; Pesliakas, Henrikas; Nainys, Juozas; Gedvilaite, Alma

    2015-06-01

    Diseases associated with porcine circovirus type 2 (PCV2) infection are having a severe economic impact on swine-producing countries. The PCV2 capsid (Cap) protein expressed in eukaryotic systems self-assemble into virus-like particles (VLPs) which can serve as antigens for diagnostics or/and as vaccine candidates. In this work, conventional adsorbents as well as a monolithic support with large pore sizes were examined for the chromatographic purification of PCV2 Cap VLPs from clarified yeast lysate. Q Sepharose XL was used for the initial separation of VLPs from residual host nucleic acids and some host cell proteins. For the further purification of PCV2 Cap VLPs, SP Sepharose XL, Heparin Sepharose CL-6B and CIMmultus SO3 monolith were tested. VLPs were not retained on SP Sepharose XL. The purity of VLPs after chromatography on Heparin Sepharose CL-6B was only 4-7% and the recovery of VLPs was 5-7%. Using ion-exchange chromatography on the CIMmultus SO3 monolith, PCV2 Cap VLPs with the purity of about 40% were obtained. The recovery of VLPs after chromatography on the CIMmultus SO3 monolith was 15-18%. The self-assembly of purified PCV2 Cap protein into VLPs was confirmed by electron microscopy. Two-step chromatographic purification procedure of PCV2 Cap VLPs from yeast lysate was developed using Q Sepharose XL and cation-exchange CIMmultus SO3 monolith. PMID:25910233

  7. Monitoring of N-nitrosodiethanolamine in cosmetic products by ion-pair complex liquid chromatography and identification with negative ion electrospray ionization mass spectrometry

    Microsoft Academic Search

    Alireza Ghassempour; Monireh Abbaci; Zahra Talebpour; Bernhard Spengler; Andreas Römpp

    2008-01-01

    A high-performance liquid chromatographic (HPLC) method was developed for the determination of N-nitrosodiethanolamine (NDELA), which is a non-volatile N-nitrosoamine. In this method, sodium 1-octanesulfonate has been used as an ion complexation agent for NDELA. The resulting complex was analyzed by reversed-phase high-performance liquid chromatography (RP-HPLC) using a Eurospher-100 C18 column (250×4.6mm, 5?m), water\\/acetonitrile (95\\/5, v\\/v) and UV detection at 234nm.

  8. A study of the analytical behaviour of selected synthetic and naturally occurring quinolines using electrospray ionisation ion trap mass spectrometry, liquid chromatography and gas chromatography and the construction of an appropriate database for quinoline characterisation

    Microsoft Academic Search

    F. O’Donnell; V. N. Ramachandran; W. F. Smyth; C. J. Hack; E. Patton

    2006-01-01

    Mass spectral fragmentation of quinoline alkaloids of significance in plants has been investigated using electrospray ionisation ion trap mass spectrometry (ESI–MSn) with a view to characterisation of molecules of unknown structure isolated from these natural sources. This investigation has led to the generation of an appropriate database incorporating data from ESI–MSn and also from gas liquid chromatography (GLC) and liquid

  9. Two-dimensional separation of ionic species by hyphenation of capillary ion chromatography × capillary electrophoresis-mass spectrometry.

    PubMed

    Beutner, Andrea; Kochmann, Sven; Mark, Jonas Josef Peter; Matysik, Frank-Michael

    2015-03-17

    The separation of complex mixtures such as biological or environmental samples requires high peak capacities, which cannot be established with a single separation technique. Therefore, multidimensional systems are in demand. In this work, we present the hyphenation of the two most important (orthogonal) techniques in ion analysis, namely, ion chromatography (IC) and capillary electrophoresis (CE), in combination with mass spectrometry. A modulator was developed ensuring a well-controlled coupling of IC and CE separations. Proof-of-concept measurements were performed using a model system consisting of nucleotides and cyclic nucleotides. The data are presented in a multidimensional contour plot. Analyte stacking in the CE separation could be exploited on the basis of the fact that the suppressed IC effluent is pure water. PMID:25708415

  10. Rapid screening method for intact glucosinolates in Chinese medicinal herbs by using liquid chromatography coupled with electrospray ionization ion trap mass spectrometry in negative ion mode.

    PubMed

    Lee, Kim-Chung; Chan, Wan; Liang, Zhitao; Liu, Ning; Zhao, Zhongzhen; Lee, Albert Wai-Ming; Cai, Zongwei

    2008-09-01

    An optimized method using liquid chromatography coupled with electrospray ionization ion trap mass spectrometry (LC/ESI-ITMS) in negative ion mode has been developed for screening different structural classes of intact glucosinolates in six Chinese medicinal herbs. The glucosinolates were extracted with hot methanol/water (70:30 v/v) and separation of the individual glucosinolates was achieved using a reversed-phase C18 column with an aqueous ammonium acetate/methanol gradient. Identification of the intact glucosinolates was based on the detection of compounds with a constant neutral loss of 242 Da corresponding to the combined loss of anhydroglucose (162 Da) and sulfur trioxide (80 Da) in collision-induced dissociation. The structures of the identified glucosinolates were confirmed with the use of group-specific product ions at m/z 195, 241, 259, 275 in their corresponding MS/MS product ion spectra. Differentiation of intact glucosinolates was achieved through their respective retention times and molecular masses as well as the characteristic product ions. The limits of detection were at the low nanogram level per injection, based on constant neutral loss scans. Significant variation in the compositions of intact glucosinolates was identified in the cruciferous herbs. This method was applied in the differentiation and quality control of two pairs of easily confused herbs. PMID:18711760

  11. Continuous processing of recombinant proteins: integration of refolding and purification using simulated moving bed size-exclusion chromatography with buffer recycling.

    PubMed

    Wellhoefer, Martin; Sprinzl, Wolfgang; Hahn, Rainer; Jungbauer, Alois

    2014-04-11

    Continuous processing of recombinant proteins was accomplished by combining continuous matrix-assisted refolding and purification by tandem simulated moving bed (SMB) size-exclusion chromatography (SEC). Recombinant proteins, N(pro) fusion proteins from inclusion bodies were dissolved with NaOH and refolded in the SMB system with a closed-loop set-up with refolding buffer as the desorbent buffer and buffer recycling of the refolding buffer of the raffinate by tangential flow filtration. For further purification of the refolded proteins, a second SMB operation also based on SEC was added. The whole system could be operated isocratically with refolding buffer as the desorbent buffer, and buffer recycling could also be applied in the purification step. Thus, a significant reduction in buffer consumption was achieved. The system was evaluated with two proteins, the N(pro) fusion pep6His and N(pro) fusion MCP-1. Refolding solution, which contained residual N(pro) fusion peptide, the cleaved autoprotease N(pro), and the cleaved target peptide was used as feed solution. Full separation of the cleaved target peptide from residual proteins was achieved at a purity and recovery in the raffinate and extract, respectively, of approximately 100%. In addition, more than 99% of the refolding buffer of the raffinate was recycled. A comparison of throughput, productivity, and buffer consumption of the integrated continuous process with two batch processes demonstrated that up to 60-fold higher throughput, up to 180-fold higher productivity, and at least 28-fold lower buffer consumption can be obtained by the integrated continuous process, which compensates for the higher complexity. PMID:24630055

  12. Hollow fiber flow field-flow fractionation and size-exclusion chromatography with MALS detection: A complementary approach in biopharmaceutical industry.

    PubMed

    Marassi, V; Roda, B; Zattoni, A; Tanase, M; Reschiglian, P

    2014-10-30

    Monoclonal antibodies (mAbs) are promising reagents both for the manufacture of drug substances and for their employment as a drug themselves, but to be approved for utilization, according to FDA recommendations and WHO guidelines, they have to undergo verifications regarding their purity, stability and percentage of aggregates. Moreover, stability tests of lots have to be performed in order to verify molecular size distribution over time and lot-to-lot consistency. Recent works in literature have highlighted the need for suitable, sensitive and reliable complementary analytical techniques for the characterization of mAbs and quantification of aggregates. Size-exclusion chromatography (SEC) is the reference technique in the biopharmaceutical industry for its robustness, high performance and simple use; however it presents some limitations especially toward the separation and detection of aggregates with high molecular weight. On the other hand, flow field-flow fractionation (F4) in its miniaturized version (hollow fiber flow field-flow fractionation, HF5) shows comparable performances with interesting additional advantages: a broad size range, gentle separation mechanism with low dilution factor and higher sensitivity. To propose HF5 as a complementary technique for evaluating aggregates' content in mAbs samples, a comparative study of both SEC and HF5 performances has been made. In this work, SEC and HF5 were coupled with UV and multi-angle light scattering detection and employed first in separating standard samples of proteins mixture used as a sample model. Then, a screening of mobile phases and an evaluation of separation performances was performed on a therapeutic mAbs formulation, demonstrating the complementarities between SEC and HF5 and their possible use as a separative platform approach for the characterization and quality control of protein drugs. PMID:25468501

  13. Chemical characterization of the ambient organic aerosol soluble in water: 2. Isolation of acid, neutral, and basic fractions by modified size-exclusion chromatography

    NASA Astrophysics Data System (ADS)

    Sullivan, Amy P.; Weber, Rodney J.

    2006-03-01

    A method employing size-exclusion chromatography (SEC) with Total Organic Carbon detection is developed to isolate and quantify the water-soluble organic carbon (WSOC) component of ambient aerosol particles by acid, neutral, and basic functional groups. The method provides unique quantitative insights into the characteristics and possible sources of a large fraction of the organic aerosol. The SEC is combined with a XAD-8 method that separates WSOC into hydrophilic and hydrophobic fractions. Calibrations show the hydrophilic fraction separates into short-chain aliphatic acids (WSOCxp_a), neutrals (WSOCxp_n, e.g., saccharides, polyols, and short-chain carbonyls), and organic bases. Recovered hydrophobic fractions are separated into acids (WSOCxrr_a, e.g., aromatic) and neutrals (WSOCxrr_n, e.g., phenols). 13Carbon-nuclear magnetic resonance on ambient samples support the calibration-based conclusions; however, calibrations only provide a guide to the type of ambient organic compounds expected in each group. Comparisons are made between XAD-8/SEC results from urban Atlanta summer and winter and biomass burning samples. The largest isolated fraction of Atlanta summer WSOC is WSOCxp_a (29% ?g C/?g C), suggesting aliphatic acids of less than C4 or C5 are the dominant secondary organic aerosol product. Combined with WSOCxrr_a, these acid groups are a higher fraction of summer organic carbon (20%) than winter (14%). They are correlated with each other (R2 = 0.74), with WSOCxp_n (R2 = 0.61 and 0.52), and with gaseous 24-hour averaged volatile organic compounds linked to mobile sources. In biomass burning samples, neutrals (WSOCxp_n and WSOCxrr_n) dominate the WSOC. Atlanta winter samples have characteristics that appear to be a combination of summer and biomass samples.

  14. Branched polymers characterized by comprehensive two-dimensional separations with fully orthogonal mechanisms: molecular-topology fractionation×size-exclusion chromatography.

    PubMed

    Edam, Rob; Mes, Edwin P C; Meunier, David M; Van Damme, Freddy A; Schoenmakers, Peter J

    2014-10-31

    Polymer separations under non-conventional conditions have been explored to obtain a separation of long-chain branched polymers from linear polymers with identical hydrodynamic size. In separation media with flow-through channels of the same order as the size of the analyte molecules in solution, the separation and the elution order of polymers are strongly affected by the flow rate. At low flow rates, the largest polymers are eluted last. At high flow rates, they are eluted first. By tuning the channel size and flow rate, conditions can be found where separation becomes independent of molar mass or size of linear polymers. Long-chain branched polymers did experience lower migration rates under these conditions and can be separated from linear polymers. This type of separation is referred to as molecular-topology fractionation (MTF) at critical conditions. Separation by comprehensive two-dimensional molecular-topology fractionation and size-exclusion chromatography (MTF×SEC) was used to study the retention characteristics of MTF. Branching selectivity was demonstrated for three- and four-arm "star" polystyrenes of 3-5×10(6)g/mol molar mass. Baseline separation could be obtained between linear polymer, Y-shaped molecules, and X-shaped molecules in a single experiment at constant flow rate. For randomly branched polymers, the branching selectivity inevitably results in an envelope of peaks, because it is not possible to fully resolve the huge numbers of different branched and linear polymers of varying molar mass. It was concluded that MTF involves partial deformation of polymer coils in solution. The increased coil density and resistance to deformation can explain the different retention behavior of branched molecules. PMID:25282310

  15. APPLICATION OF GC/ITD (GAS CHROMATOGRAPHY/ION TRAP DETECTOR) TO ENVIRONMENTAL ANALYSIS (JOURNAL VERSION)

    EPA Science Inventory

    The choice of gas chromatography (GC) detectors has expanded rapidly. The necessity for mass spectrometric (MS) characterization of GC effluents stems from the complexity of the matrices associated with environmental samples. There are currently several MS types being used in con...

  16. Determination of anionic minerals in black and kombucha tea using ion chromatography

    Microsoft Academic Search

    Sangita D. Kumar; G. Narayan; S. Hassarajani

    2008-01-01

    A simple, rapid and accurate method for the determination of anionic minerals in tea brew has been developed. The quantitative determination of anions – fluoride, chloride, bromide, iodide, nitrate, phosphate and sulphate was accomplished by anion exchange chromatography with conductometric detection. A Metrosep Anion Dual 2 analytical column connected in series with a Metrosep RP guard column was used for

  17. Novel algorithm for simultaneous component detection and pseudo-molecular ion characterization in liquid chromatography-mass spectrometry.

    PubMed

    Zhang, Yufeng; Wang, Xiaoan; Wo, Siukwan; Ho, Hingman; Han, Quanbin; Fan, Xiaohui; Zuo, Zhong

    2015-01-01

    Resolving components and determining their pseudo-molecular ions (PMIs) are crucial steps in identifying complex herbal mixtures by liquid chromatography-mass spectrometry. To tackle such labor-intensive steps, we present here a novel algorithm for simultaneous detection of components and their PMIs. Our method consists of three steps: (1) obtaining a simplified dataset containing only mono-isotopic masses by removal of background noise and isotopic cluster ions based on the isotopic distribution model derived from all the reported natural compounds in dictionary of natural products; (2) stepwise resolving and removing all features of the highest abundant component from current simplified dataset and calculating PMI of each component according to an adduct-ion model, in which all non-fragment ions in a mass spectrum are considered as PMI plus one or several neutral species; (3) visual classification of detected components by principal component analysis (PCA) to exclude possible non-natural compounds (such as pharmaceutical excipients). This algorithm has been successfully applied to a standard mixture and three herbal extract/preparations. It indicated that our algorithm could detect components' features as a whole and report their PMI with an accuracy of more than 98%. Furthermore, components originated from excipients/contaminants could be easily separated from those natural components in the bi-plots of PCA. PMID:25467485

  18. Large-scale Preparation of ?-Lactoglobulin A and B by Ultrafiltration and Ion-exchange Chromatography

    Microsoft Academic Search

    K. R. Kristiansen; J. Otte; R. Ipsen; K. B. Qvist

    1998-01-01

    Purification of ?-lactoglobulin A and B was carried out by ultrafiltration and anion-exchange chromatography under very gentle conditions; temperature and pH did not exceed 50°C and 7.0, respectively, at any step of the process. Fresh, raw milk from cows homozygotic in ?-lactoglobulin A or B was used. Two batches of ?-lactoglobulin B, 485 and 125g, and one batch of ?-lactoglobulin

  19. CRC handbook of chromatography

    SciTech Connect

    Qureshi, M.

    1986-01-01

    This book provides technology for routine analysis or developing new methods of chromatography or organic materials. In this book Section 1 presents the principles, techniques, quantitative determinations and detection methods used in chromatographic analysis. In the major part of the book, Section 2 summarizes data in voluminous tabular/graphic form on paper, thin layer, liquid and gas chromatography. Section 3 lists important books on electrophoreses, gel permeation chromatography, and ion exchange, in addition to the other forms of chromatography.

  20. On-line preconcentration and separation of neutral and charged aromatic compounds by ion interaction chromatography

    Microsoft Academic Search

    Corrado Sarzanini; Maria Concetta Bruzzoniti; Giovanni Sacchero; Edoardo Mentasti

    1996-01-01

    An ion-interaction based chromatographic procedure was developed for the on-line preconcentration, separation and UV detection of benzene and naphthalene sulphonic derivatives having different charges. The retention behaviour of the species was studied on an octylsilica stationary phase, using cetyltrimethylammonium chloride (CTACl) as ion pair reagent and methanol as organic modifier in the presence of sodium chloride. The effect of CTACl,

  1. Determination of fluorine, chlorine and bromine in household products by means of oxygen bomb combustion and ion chromatography.

    PubMed

    Zhang, Shuai; Zhao, Tianbo; Wang, Jia; Qu, Xiaoling; Chen, Wei; Han, Yin

    2013-01-01

    A method for routine determination of fluorine, chlorine and bromine in household products was developed and validated. In this work, halogen analyses were made based on oxygen bomb combustion followed by ion chromatography (IC). The chromatographic analysis was performed by an IonPac AS19 hydroxide-selective anion-exchange column, a reagent free ion chromatograph eluent generator and an anion self-regenerating suppressor in 10 min. The response was linear (r ? 0.9995) in the entire investigated domain. The limit of detection for the halogens was in the range of 2 to 9 × 10(-3) mg/L and the limit of quantification was lower than 8 mg/Kg with 20 µL of injection volume. The certified reference material of ERM-EC 681k was pretreated using an oxygen bomb combustion procedure to demonstrate the precision of the proposed method. The quantitative analysis results obtained by IC for the target elements were 797 ± 9 mg/Kg chlorine and 786 ± 25 mg/Kg bromine, which were in good agreement with the certified values of 800 ± 4 mg/Kg chlorine, 770 ± 5 mg/Kg bromine for ERM-EC 681k, respectively. This validated method was successfully applied for the analysis of fluorine, chlorine and bromine in household product samples, and the variation of halogen contained among the tested samples was remarkable. PMID:22752184

  2. The novel use of gas chromatography-ion mobility-time of flight mass spectrometry with secondary electrospray ionization for complex mixture analysis

    Microsoft Academic Search

    Christina L. Crawford; Stephan Graf; Marc Gonin; Katrin Fuhrer; Xing Zhang; Herbert H. Hill Jr

    2011-01-01

    Increasing the dimensionality of an analysis enables more detailed and comprehensive investigations of complex mixtures. One\\u000a dimensional separation techniques like gas chromatography (GC) and ion mobility spectrometry (IMS) provide limited chemical\\u000a information about complex mixtures. The combination of GC, ion mobility spectrometry, and time-of-flight mass spectrometry\\u000a (GC-IM-TOFMS) provides three-dimensional separation of complex mixtures. In this work, a hybrid GC-IM-TOFMS with

  3. The effect of liquid chromatography eluents and additives on the positive ion responses of cocaine, benzoylecgonine, and ecgonine methyl ester using electrospray ionization

    Microsoft Academic Search

    Patrick M. Jeanville; Estela S. Estapé; Ivette Torres-Negrón de Jeanville

    2003-01-01

    We investigated the effect of common chromatography eluents and additives on the positive ion responses of ecgonine methyl ester (EME), benzoylecgonine (BZE), and cocaine (COC) using electrospray ionization (ESI). Primarily [M+H]+ ions were observed, although decomposition of EME and COC to ecgonidine methyl ester gave a sizable peak at m\\/z 182.0. The results showed that the sensitivity for the test

  4. Analysis of Oligo-?-carrageenan by Reversed Phase Ion-pair Ultra Performance Liquid Chromatography Coupled with Electrospray Ionization-Time of Flight-Mass Spectrometry

    Microsoft Academic Search

    Yang GAO; Hai-Min CHEN; Ji-Lin XU; De-Ying CHEN; Xiao-Jun YAN

    2009-01-01

    The reverse phase ion-pair ultra performance liquid chromatography coupled with electrospray ionization time of flight mass spectrometry (RPIP-UPLC-ESI-Q-TOF-MS) method was developed for the analyses and elucidation of sulfated oligosaccharides. Mass spectra were obtained by ESI-Q-TOF-MS in both positive and negative ionization modes. Oligo-?-carrageenans were separated on BEH C18 column using heptylamine (20 mM, pH 4) as the ion-pairing reagent and

  5. Application of Doehlert design in optimizing the determination of degraded products of nerve agents by ion-pair liquid chromatography electrospray ionization tandem mass spectrometry

    Microsoft Academic Search

    Vijay Tak; Pankaj K. Kanaujia; Deepak Pardasani; Rajesh Kumar; R. K. Srivastava; A. K. Gupta; D. K. Dubey

    2007-01-01

    A qualitative method was developed for the determination of degraded products of nerve agents by using ion-pair liquid chromatography electrospray ionization tandem mass spectrometry (IP-LC–ESI-MSn). Generally, alkylphosphonic acids (APAs) and O-alkyl alkylphosphonic acids (AAPAs) give deprotonated molecular ion [M?H]? in negative mode. Interestingly, first time we obtained the molecular radical anion [M]? of phosphonic acids in negative mode by using

  6. pH-gradient ion-exchange chromatography: an analytical tool for design and optimization of protein separations.

    PubMed

    Ahamed, Tangir; Nfor, Beckley K; Verhaert, Peter D E M; van Dedem, Gijs W K; van der Wielen, Luuk A M; Eppink, Michel H M; van de Sandt, Emile J A X; Ottens, Marcel

    2007-09-14

    This work demonstrates that a highly linear, controllable and wide-ranged pH-gradient can be generated through an ion-exchange chromatography (IEC) column. Such a pH-gradient anion-exchange chromatography was evaluated with 17 model proteins and found that acidic (pI<6) and basic (pI>8) proteins elute roughly at their pI, whereas neutral proteins (pI 6-8) elute at pH 8-9 regardless their pI values. Because of the flat nature of protein titration curves from pH approximately 6 to approximately 9, neutral proteins indeed exhibit nearly zero net charge at pH approximately 9. The elution-pH in pH-gradient IEC or the titration curve, but not the pI, was identified as the key parameter for pH optimization of preparative IEC in a fast and rational way. The pH-gradient IEC was also applied and found to be an excellent analytical tool for the fractionation of crude protein mixtures. PMID:17673242

  7. A solid phase extraction-ion chromatography with conductivity detection procedure for determining cationic surfactants in surface water samples.

    PubMed

    Olkowska, Ewa; Polkowska, ?aneta; Namie?nik, Jacek

    2013-11-15

    A new analytical procedure for the simultaneous determination of individual cationic surfactants (alkyl benzyl dimethyl ammonium chlorides) in surface water samples has been developed. We describe this methodology for the first time: it involves the application of solid phase extraction (SPE-for sample preparation) coupled with ion chromatography-conductivity detection (IC-CD-for the final determination). Mean recoveries of analytes between 79% and 93%, and overall method quantification limits in the range from 0.0018 to 0.038 ?g/mL for surface water and CRM samples were achieved. The methodology was applied to the determination of individual alkyl benzyl quaternary ammonium compounds in environmental samples (reservoir water) and enables their presence in such types of waters to be confirmed. In addition, it is a simpler, less time-consuming, labour-intensive, avoiding use of toxic chloroform and significantly less expensive methodology than previously described approaches (liquid-liquid extraction coupled with liquid chromatography-mass spectrometry). PMID:24148395

  8. Characterization of column packing materials in high-performance liquid chromatography by charge-detection quadrupole ion trap mass spectrometry.

    PubMed

    Xiong, Caiqiao; Zhou, Xiaoyu; Chen, Rui; Zhang, Yiming; Peng, Wen-Ping; Nie, Zongxiu; Chang, Huan-Cheng; Liu, Huwei; Chen, Yi

    2011-07-01

    This article reports an application of charge-detection quadrupole ion trap mass spectrometry (CD-ITMS) to characterize the column packing materials in high-performance liquid chromatography (HPLC). Both the mean mass and the mass distribution of the packing materials are obtained and used to calculate the specific surface area of unbonded silica, the carbon load of the bonded silica, and their particle size distributions. The obtained specific surface areas and carbon loads are consistent with those measured independently by nitrogen sorption and elemental analysis respectively, whereas the derived size distributions show better resolution than that measured by a laser particle size analyzer. Furthermore, we evaluate the uniformity of particle size, which is the key parameter for column efficiency of the liquid chromatography by analyzing the mass distribution of the packing materials at the top and bottom of the column. A broader mass distribution, which yields decreased column efficiency, is observed for the column top because of the excessive use of the column. Our results suggest that CD-ITMS can serve as an alternative means for the characterization of the packing materials in HPLC and is potentially useful for column quality control. PMID:21612293

  9. Identification and quantitation of auxins in plants by liquid chromatography/electrospray ionization ion trap mass spectrometry.

    PubMed

    Lu, Qiaomei; Zhang, Lan; Chen, Tianwen; Lu, Minghua; Ping, Tong; Chen, Guonan

    2008-08-01

    Auxin is an important phylohormone, which regulates specific physiological responses such as division, elongation and differentiation of cells. A new method using liquid chromatography/electrospray ionization ion trap mass spectrometry (LC/ESI-ITMS) has been developed for identification and quantitation of four auxins. Under the optimum conditions, four auxins (indole-3-acetic acid, indole-3-propionic acid, indole-3-butyric acid and 1-naphthylacetic acid) were completely separated and quantitated within 7 min with a minimum detection limit of 8.0 ng mL(-1) with relative standard deviations lower than 5.0%. This method also has been applied to analysis of auxins in Chinese cabbage where, even with a complicated serious background perturbation due to the natural biological matrix, the mean recoveries ranged from 77.5% to 99.8%. Finally, we discuss the MS-relevant properties of the identified auxins in detail. PMID:18655000

  10. Closed tube sample introduction for gas chromatography–ion mobility spectrometry analysis of water contaminated with a chemical warfare agent surrogate compound

    Microsoft Academic Search

    Richard P. Erickson; Ashish Tripathi; Waleed M. Maswadeh; A. Peter Snyder; Philip A. Smith

    2006-01-01

    Ion mobility spectrometry (IMS) is a proven technology for detection of vapor phase chemical warfare agents. The technology is suitable for field portable instrumentation due to its small size, high sensitivity, speed of analysis, and low power consumption. However, it suffers from a limited dynamic range and potential difficulties in identifying compounds in complex matrices. The use of gas chromatography

  11. EVALUATION OF GAS CHROMATOGRAPHY COUPLED WITH ION MOBILITY SPECTROMETRY FOR MONITORING VINYL CHLORIDE AND OTHER CHLORINATED AND AROMATIC COMPOUNDS IN AIR SAMPLES

    EPA Science Inventory

    The objective of this research was to evaluate, in the laboratory, the potential of gas chromatography/ion mobility spectrometry (GC/IMS) for monitoring vinyl chloride and other organic compounds in air samples in the field. It was determined that GC/IMS has the potential to dire...

  12. DETERMINATION OF A BOUND MUSK XYLENE METABOLITE IN CARP HEMOGLOBIN AS A BIOMARKER OF EXPOSURE BY GAS CHROMATOGRAPHY MASS SPECTROMETRY USING SELECTED ION MONITORING

    EPA Science Inventory

    Musk xylene (MX) is widely used as a fragrance ingredient in commercial toiletries. Identification and quantification of a bound 4-amino-MX (AMX) metabolite was carried out by gas chromatography-mass spectrometry (GC/MS), with selected ion monitoring (SIM). Detection of AMX occur...

  13. Speciation of arsenic(III)/arsenic(V) and selenium(IV)/ selenium(VI) using coupled ion chromatography - hydride generation atomic absorption spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Simple analytical methods have been developed to speciate inorganic arsenic and selenium in the ppb range using coupled ion chromatography-hydride generation atomic absorption spectrometry. Because of the differences in toxicity and adsorption behavior, determinations of the redox states arsenite A...

  14. Multi-residue contaminants and pollutants analysis in saffron spice by stir bar sorptive extraction and gas chromatography–ion trap tandem mass spectrometry

    Microsoft Academic Search

    Luana Maggi; Manuel Carmona; C. Priscila del Campo; Amaya Zalacain; Jorge Hurtado de Mendoza; Francisco A. Mocholí; Gonzalo L. Alonso

    2008-01-01

    A method for the simultaneous determination of 46 semi-volatile organic contaminants and pollutants in saffron has been developed for the first time using a stir bar sorptive extraction technique and thermal desorption in combination with gas chromatography–ion trap tandem mass spectrometry. The analytical method proposed was easy, rapid and sensitive and showed good linearity, accuracy, repeatability and reproducibility over the

  15. Liquid chromatography quadrupole linear ion trap mass spectrometry for multiclass screening and identification of lipophilic marine biotoxins in bivalve mollusks.

    PubMed

    Wu, Haiyan; Guo, Mengmeng; Tan, Zhijun; Cheng, Haiyan; Li, Zhaoxin; Zhai, Yuxiu

    2014-09-01

    A liquid chromatography quadrupole linear ion trap mass spectrometry method with fast polarity switching and a scheduled multiple reaction monitoring algorithm mode was developed for multiclass screening and identification of lipophilic marine biotoxins in bivalve molluscs. A major advantage of the method is that it can detect members of all six groups of lipophilic marine biotoxins [okadaic acid (OA), yessotoxins (YTX), azaspiracids (AZA), pectenotoxins (PTX), cyclic imines (CI), and brevetoxins (PbTx)], thereby allowing quantification and high confidence identification from a single liquid chromatography tandem mass spectrometry (LC-MS/MS) injection. An enhanced product ion (EPI) library was constructed after triggered collection of data via information-dependent acquisition (IDA) of EPI spectra from standard samples. A separation method for identifying 17 target toxins in a single analysis within 12min was developed and tested. Different solid phase extraction sorbents, the matrix effect (for oyster, scallop, and mussel samples), and stability of the standards also were evaluated. Matrix-matched calibration was used for quantification of the toxins. The limits of detection were 0.12-13.6?g/kg, and the limits of quantification were 0.39-45.4?g/kg. The method was used to analyze 120 shellfish samples collected from farming areas along the coast of China, and 7% of the samples were found to be contaminated with toxins. The library search identified PbTx-3, YTX, OA, PTX2, AZA1, AZA2, and desmethylspirolide C (SPX1). Overall, the method exhibited excellent sensitivity and reproducibility, and it will have broad applications in the monitoring of lipophilic marine biotoxins. PMID:25086754

  16. Capability measurement of size-exclusion chromatography with a light-scattering detection method in a stability study of bevacizumab using the process capability indices.

    PubMed

    Oliva, Alexis; Llabrés, Matías; Fariña, José B

    2014-08-01

    In this study, we investigated if the size-exclusion chromatography coupled with light-scattering and refractive index detection (SEC/LS/RI) method is fitted for its intended purpose and checked if the analytical method is able to provide enough conforming results. For this, the process capability indices Cp, Cpk, and Cpm were computed. The traditional X-chart and moving range (MR) chart were used by the same analyst to monitor the equipment in the laboratory over a 1-year period. For this, a bovine serum albumin (BSA) sample (0.3 mg mL(-1)) with a nominal Mw of 66.4 kDa was analyzed each working day. The results confirmed that the analytical method is in-control and stable. To determine whether the given process meets the present capability requirement and runs under the desired quality conditions, the Pearn and Shu (2003) method based on the lower confidence bound C on Cpm was used. The estimator Cpm was 1.81, and the lower confidence bound C was 1.40. We therefore conclude that the true value of the method capability Cpm is no less than 1.40 with a 95% level of confidence. This result indicates that the method is satisfactory and no stringent precision control is required. The usefulness of this method was applied in the characterization of bevacizumab commercial pharmaceutical preparations stored under different conditions that lead to aggregation. In this case, the computed Cpm index was 0.98 (0.70, 1.26), which indicates that the method does not comply with the specification limits and needs to be revised. The quality improvement effort should: (1) reduce the uncertainty in the absolute Mw determination; (2) either move the process mean closer to the target value or reduce the process variation, i.e. improve the method accuracy (?-T) and precision (?(2)). On this point, the Bayesian posterior distribution of the mean and standard deviation pointed out the need to control the precision but specially accuracy in order to reduce the overall uncertainty of analytical method and thus, the method is capable. PMID:24786652

  17. SEPARATION OF PROTEINS BY ION EXCHANGE AND MEMBRANE CHROMATOGRAPHY: BUFFER COMPOSITION, INTERFERING IMPURITIES AND FOULING CONSIDERATIONS

    E-print Network

    Imam, Tahmina

    2010-01-16

    solution properties (pH, ionic strength, buffer ions) in order to maximize lysozyme purification by a strong cation exchange resin. The interaction of phytic acid, a major impurity, present in transgenic rice extracts, that contributes to decreased lysozyme...

  18. Ligand-Exchange Chromatography of Aromatic Amines on Resin-Bound Cobalt Ion

    Microsoft Academic Search

    Erol Pehlivan; Ufuk S. Vural; Ahmet Ayar; Salih Yildiz

    1996-01-01

    The use of cobalt metal for the selective separation of aromatic amines is completed with a chemically bonded diamine and glyoxime functional groups onto Lycopodium clavatum. Oximes and amines are excellent complexing agents for transition metal ions. Cobalt(II) metal ions can easily be immobilized on bis-diami-noethyl-glyoximated sporopollenin (bDAEG-sporopollenin). The ligand-exchange behavior of modified Lycopodium clavatum with respect to aromatic amines

  19. Quantification of Suramin by Reverse-Phase Ion-Pairing High-Performance Liquid Chromatography

    Microsoft Academic Search

    Raymond W. Klecker Jr; Jerry M. Collins

    1985-01-01

    A specific and sensitive method has been developed for the separation and quantification of suramin and trypan blue (internal standard) in human plasma. Plasma samples were extracted by centrifugation after the addition of ion-pairing reagent (tetra-butylammonium phosphate, TRAP) and methanol. Extracts were injected directly onto a reverse-phase ion-pairing HPLC system with 5 mM TBAP in the mobile phase. There was

  20. Ion exchange chromatography and radioimmunoassay procedure for measuring opioid peptides and substance P

    SciTech Connect

    Bergstroem, L.; Christensson, I.; Folkesson, R.; Stenstroem, B.; Terenius, L.

    1983-10-01

    The measurements of peptides of the enkephalin, dynorphin and substance P systems is complicated by the number of possible precursor fragments and degradation products that might cross-react with the antisera. By using an ion-exchanger step before radioimmunoassay one can reduce the possibility that observed peptide levels are due to precursors or metabolites. The ion-exchanger method runs with good recovery and its main advantage is that many samples can be run in parallel. The recovery from the ion-exchanger was similar using two different homogenizing media, whereas the measured endogenous levels of (Met) and (Leu)enkephalin were 3-4 fold higher with 1M acetic acid than when a 1:1 MeOH/HCl mixture was used for tissue extraction.

  1. Chromatography and the hundred year mystery of inorganic ions at aqueous interfaces: adsorption of inorganic ions at the Porous Graphitic Carbon Aqueous Interface follows the Hofmeister series.

    PubMed

    Cecchi, Teresa; Marcotulli, Federica

    2013-11-01

    Many physical phenomena are affected by the structure of water interfaces, yet it remains an active and controversial subject. A great deal of recent theoretical endeavour and computer simulations question the validity of the Onsager Samaras theory of the ion-free interface between an electrolyte solution and an hydrophobic surface. Experimental results play a crucial role in assessing the legitimacy of the theories. Experimental data are scarce, while simulation results suggest an increasing surface affinity of ions with increasing chaotropic character, in dramatic contradiction to the classical view. Chromatography is a powerful separative technique, but we originally used it as a tool to detect the adsorption of chloride electrolytes and sodium electrolytes, strongly expected to shun any dielectric boundary, onto an hydrophobic surface, and to rank ions according to their adsorbophilicities. Frontal analysis gave unequivocal experimental evidence to this unexpected phenomenon and it was used to quantify it. The infinite dilution equilibrium constants for adsorption of kosmotropes and chaotropes onto the interface were obtained and contrasted to the Jones-Dole B viscosity coefficients, that is a common quantifier of the Hofmeister effect. It is clear that (i) the more chaotropic the ion is, the more it contributes to the global adsorbophilicity of the electrolyte; (ii) the influence of the variable anion is more than twofold that of the variable cation, thereby confirming a robust observation in many other physical systems. Standard free energy of adsorption for each electrolyte was calculated and its reliability was commented upon. The central issue in this paper is the effective and ascertained adsorption of electrolytes onto an hydrophobic surface and the fact that the adsorbophilicity of an electrolyte may be inferred from its position in the Hofmeister series. PMID:24075459

  2. On-line ion-pair solid-phase extraction-liquid chromatography-mass spectrometry for the analysis of quaternary ammonium herbicides.

    PubMed

    Castro, R; Moyano, E; Galceran, M T

    2000-02-11

    An ion-pair on-line solid-phase extraction procedure using C8 extraction disks, suitable for liquid chromatography-mass spectrometry analysis is developed to determine quaternary ammonium herbicides (quats) in water samples. The separation of these compounds was performed using ion-pair chromatography with heptafluorobutyric acid (15 mM, pH 3.3) and acetonitrile gradient elution. Detection was carried out using a quadrupole mass spectrometer. Water sample volumes up to 50 ml can be preconcentrated with recoveries higher than 70%. Good precision and accuracy (day-to-day and run-to-run) were obtained and the detection limits ranged from 6 to 85 ng l(-1). The proposed on-line ion-pair solid-phase method enables compliance with European Community directives for drinking waters (100 ng l(-1)). PMID:10720257

  3. Simultaneous determination of 13 components in oxidative hair dyes by high-performance chromatography using an ion-pair reagent.

    PubMed

    Lai, Ying; Wang, Honghui; Dong, Qingmu; Chen, Hexiu; Lin, Rui; Cai, Yanping

    2012-01-01

    A reliable high-performance liquid chromatography (HPLC) method was developed for the simultaneous determination of 13 dye intermediates, including benzenediamines, aminophenols, benzenediols, naphthalenediol, and diaminopyridine, in oxidative hair dyes. Samples were extracted with 50% ethanol by adding sodium dithionite to prevent oxidation. The influences of buffer type, buffer pH, ion-pair reagent, and elution gradient were studied. A C18 column with aqueous compatibility and acetonitrile-citric acid mobile phase system (pH 2.6) with sodium 1-octanesulfonate as ion-pair reagent were selected for the separation of target compounds. Detection was performed by a diode array detector, (DAD) and two different wavelengths (280 and 331 nm) were used for quantification. Results showed that 13 dye intermediates got good separation within 25 min. The detection limits of these compounds were in the range of 0.2-2 mg/l. The calibration curves were linear within 2-500 mg/l with 0.999 as a typical correlation coefficient. The recoveries of target compounds in hair dyes ranged from 81.7% to 102.0% with four addition levels. The method described was validated by five different laboratories and successfully applied to the analysis of commercial oxidative hair dyes. PMID:23089354

  4. Ion chromatography-mass spectrometry: a review of recent technologies and applications in forensic and environmental explosives analysis.

    PubMed

    Barron, Leon; Gilchrist, Elizabeth

    2014-01-01

    The development and application of ion chromatography (IC) coupled to mass spectrometry (MS) is discussed herein for the quantitative determination of low-order explosives-related ionic species in environmental and forensic sample types. Issues relating to environmental explosives contamination and the need for more confirmatory IC-MS based applications in forensic science are examined. In particular, the compatibility of a range of IC separation modes with MS detection is summarised along with the analytical challenges that have been overcome to facilitate determinations at the ng-?g L(-1) level. Observed trends in coupling IC to inductively coupled plasma and electrospray ionisation mass spectrometry form a particular focus. This review also includes a discussion of the relative performance of reported IC-MS methods in comparison to orthogonal ion separation-based, spectrometric and spectroscopic approaches to confirmatory detection of low-order explosives. Finally, some promising areas for future research are highlighted and discussed with respect to potential IC-MS applications. PMID:24331039

  5. Investigation of the preparation and use of low-capacity anion exchangers in single-column ion chromatography

    SciTech Connect

    Barron, R.E.

    1984-01-01

    The preparation and uses of strong-base anion exchangers of low capacity are reviewed. A new adaptation of known reactions is presented for the reproducible preparation of Type I anion exchangers of low capacity and it is explored in some detail. The resins are based on the macroreticular copolymer known as XAD-1. It is shown that the same reaction scheme may be used on any porous styrene-divinylbenzene copolymer. Procedures are described for the preparation of twelve other strong-base resins with various structural differences in the quaternary ammonium functional group. These resins are then evaluated to determine the effect of chemical structure on selectivity for a number of common monovalent and divalent anions. It is shown that the structure of the quaternary ammonium ion has a definite effect on selectivity. It is also shown that surface modification can affect selectivity. The implications for single-column ion chromatography are discussed and some examples are given where a change in the chemical structure of the functional group is of practical value in the separation of anions. The factors influencing the choice of an eluent acid are outlined and it is shown that some acids are better than others on the basis on their lack of interaction with the copolymer matrix.

  6. The determination of the Fe sup 2+ /Fe sup 3+ ratio in simulated nuclear waste glass by ion chromatography

    SciTech Connect

    Jantzen, C.M.

    1990-10-01

    Liquid high-level nuclear waste will be immobilized at the Savannah River Site (SRS) by vitrification in borosilicate glass in the Defense Waste Processing Facility (DWPF). In this facility, control of the oxidation/reduction (redox) equilibrium in the glass melter is critical for processing of the nuclear waste. Therefore, the development of a rapid and reliable analytical method for the determination of the redox equilibrium is of considerable interest. Redox has been determined by measuring the ratio of ferrous to ferric ions in the glass melt. Two analytical techniques for glass redox measurement have been investigated for the DWPF: Mossbauer Spectroscopy which may be subject to interferences from the radiation in actual waste, and a rapid and simple chemical dissolution/spectrophotometric technique. Comparisons of these techniques have been made at several laboratories including Clemson University. In the study attached, the determination of the redox ratio by Ion Chromatography (IC) was investigated as a potential new technology. Clemson University performed IC analyses on the same glasses as previously examined by wet chemical and Mossbauer techniques. Results from all three techniques were highly correlated and IC was reported to be a promising new technology for redox measurement. 19 refs., 19 figs., 5 tabs.

  7. Ligand-exchange chromatography of aromatic amines on resin-bound cobalt ion

    SciTech Connect

    Pehlivan, E.; Vural, U.S.; Ayar, A.; Yildiz, S. [Selcuk Univ., Konya (Turkey)

    1996-06-01

    The use of cobalt metal for the selective separation of aromatic amines is completed with a chemically bonded diamine and glyoxime functional groups onto Lycopodium clavatum. Oximes and amines are excellent complexing agents for transition metal ions. Cobalt(II) metal ions can easily be immobilized on bis-diaminoethyl-glyoximated sporopollenin (bDAEG-sporopollenin). The ligand-exchange behavior of modified Lycopodium clavatum with respect to aromatic amines was investigated. This will permit the evaluation of bDAEG-sporopollenin ligand exchangers for their utilization as sorbents in the recovery, pollution control, and elimination of amines from wastewater.

  8. Development Of Ion Chromatography Methods To Support Testing Of The Glycolic Acid Reductant Flowsheet In The Defense Waste Processing Facility

    SciTech Connect

    Wiedenman, B. J.; White, T. L.; Mahannah, R. N.; Best, D. R.; Stone, M. E.; Click, D. R.; Lambert, D. P.; Coleman, C. J.

    2013-10-01

    Ion Chromatography (IC) is the principal analytical method used to support studies of Sludge Reciept and Adjustment Tank (SRAT) chemistry at DWPF. A series of prior analytical ''Round Robin'' (RR) studies included both supernate and sludge samples from SRAT simulant, previously reported as memos, are tabulated in this report.2,3 From these studies it was determined to standardize IC column size to 4 mm diameter, eliminating the capillary column from use. As a follow on test, the DWPF laboratory, the PSAL laboratory, and the AD laboratory participated in the current analytical RR to determine a suite of anions in SRAT simulant by IC, results also are tabulated in this report. The particular goal was to confirm the laboratories ability to measure and quantitate glycolate ion. The target was + or - 20% inter-lab agreement of the analyte averages for the RR. Each of the three laboratories analyzed a batch of 12 samples. For each laboratory, the percent relative standard deviation (%RSD) of the averages on nitrate, glycolate, and oxalate, was 10% or less. The three laboratories all met the goal of 20% relative agreement for nitrate and glycolate. For oxalate, the PSAL laboratory reported an average value that was 20% higher than the average values reported by the DWPF laboratory and the AD laboratory. Because of this wider window of agreement, it was concluded to continue the practice of an additional acid digestion for total oxalate measurement. It should also be noted that large amounts of glycolate in the SRAT samples will have an impact on detection limits of near eluting peaks, namely Fluoride and Formate. A suite of scoping experiments are presented in the report to identify and isolate other potential interlaboratory disceprancies. Specific ion chromatography inter-laboratory method conditions and differences are tabulated. Most differences were minor but there are some temperature control equipment differences that are significant leading to a recommendation of a heated jacket for analytical columns that are remoted for use in radiohoods. A suggested method improvement would be to implement column temperture control at a temperature slightly above ambient to avoid peak shifting due to temperature fluctuations. Temperature control in this manner would improve short and longer term peak retention time stability. An unknown peak was observed during the analysis of glycolic acid and SRAT simulant. The unknown peak was determined to best match diglycolic acid. The development of a method for acetate is summaraized, and no significant amount of acetate was observed in the SRAT products tested. In addition, an alternative Gas Chromatograph (GC) method for glycolate is summarized.

  9. Ion size effects at ionic exclusion from dielectric interfaces and slit nanopores

    E-print Network

    Sahin Buyukdagli; C. V. Achim; T. Ala-Nissila

    2011-06-02

    A previously developed field-theoretic model [R.D. Coalson et al., J. Chem. Phys. 102, 4584 (1995)] that treats core collisions and Coulomb interactions on the same footing is investigated in order to understand ion size effects on the partition of neutral and charged particles at planar interfaces and the ionic selectivity of slit nanopores. We introduce a variational scheme that can go beyond the mean-field (MF) regime and couple in a consistent way pore modified core interactions, steric effects, electrostatic solvation and image-charge forces, and surface charge induced electrostatic potential. We show that in the dilute limit, the MF and the variational theories agree well with MC simulation results, in contrast to a recent RPA method. The partition of charged Yukawa particles at a neutral dielectric interface (e.g air-water or protein-water interface) is investigated. It is shown that as a result of the competition between core collisions that push the ions towards the surface, and repulsive solvation and image forces that exclude them from the interface, a concentration peak of finite size ions sets in close to the dielectric interface. We also characterize the role played by the ion size on the ionic selectivity of neutral slit nanopores. We show that the complex interplay between electrostatic forces, excluded volume effects induced by core collisions and steric effects leads to an unexpected reversal in the ionic selectivity of the pore with varying pore size: while large pores exhibits a higher conductivity for large ions, narrow pores exclude large ions more efficiently than small ones.

  10. High-resolution determination of {sup 147}Pm in urine using dynamic ion-exchange chromatography

    SciTech Connect

    Elchuk, S.; Lucy, C.A.; Burns, K.I. [Chalk River Labs., Ontario (Canada)

    1992-10-15

    Ion exchange preconcentration followed by HPLC purification prior to scintillation counting was used to measure the concentration of {sup 147}Pm in urine. the detection limit for this method was found to be 0.1 Bq (3 fg) of {sup 147}Pm in 500 ml of urine.

  11. Integrated cation–anion\\/volatile fluid inclusion analysis by gas and ion chromatography; methodology and examples

    Microsoft Academic Search

    D. M. DeR Channer; C. J Bray; E. T. C Spooner

    1999-01-01

    Combined gas and ion chromatographic analysis of well characterized, small (?1 g) fluid inclusion-bearing samples is a powerful, but simple, means for obtaining integrated fluid concentrations of major and trace, volatile and ionic fluid constituents without using microthermometrically determined salinity for normalization. The methodology, which is described and assessed in detail, involves crushing a carefully cleaned sample at ?105°C in

  12. DETERMINATION OF BROMATE IN DRINKING WATERS BY ION CHROMATOGRAPHY WITH INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRIC DETECTION

    EPA Science Inventory

    Bromate is a disinfection by-product in drinking water, formed during the ozonation of source water containing bromide. An inductively coupled plasma mass spectrometer is combined with an ion chromatograph for the analysis of bromate in drinking waters. Three chromatographic colu...

  13. DETERMINATION OF CARBOXYLIC ACIDS BY ION-EXCLUSION CHROMATOGRAPHY WITH NON-SUPPRESSED CONDUCTIVITY AND OPTICAL DETECTORS

    EPA Science Inventory

    Determination of carboxylic acids using non-suppressed conductivity and UV detections is described. The background conductance of 1-octanesulfonic acid, hexane sulfonic acid and sulfuric acid at varying concentrations was determined. Using 0.2 mM 1-octanesulfonic acid as a mobile...

  14. DETERMINATION OF CARBOXYLIC ACIDS BY ION-EXCLUSION CHROMATOGRAPHY WITH NON-SUPPRESSED CONDUCTIVITY AND OPTICAL DETECTORS

    EPA Science Inventory

    Determination of carboxylic acids using non-suppressed conductivity and UV detections is described. he background conductance of I-octanesulfonic acid, hexane sulfonic acid and sulfuric acid at varying concentrations was determined. sing 0.2 MM I-octanesulfonic acid as a mobile p...

  15. The analysis of aqueous mixtures using liquid chromatography-electrospray mass spectrometry

    SciTech Connect

    Johnson, S.

    1999-02-12

    The focus of this dissertation is the use of chromatographic methods coupled with electrospray mass spectrometry (ES-MS) for the determination of both organic and inorganic compounds in aqueous solutions. The combination of liquid chromatography (LC) methods and ES-MS offers one of the foremost methods for determining compounds in complex aqueous solutions. In this work, LC-ES-MS methods are devised using ion exclusion chromatography, reversed phase chromatography, and ion exchange chromatography, as well as capillary electrophoresis (CE). For an aqueous sample, these LC-ES-MS and CE-ES-MS techniques require no sample preparation or analyte derivatization, which makes it possible to observe a wide variety of analytes as they exist in solution. The majority of this work focuses on the use of LC-ES-MS for the determination of unknown products and intermediates formed during electrochemical incineration (ECI), an experimental waste remediation process. This report contains a general introduction to the project and the general conclusions. Four chapters have been removed for separate processing. Titles are: Chapter 2: Determination of small carboxylic acids by ion exclusion chromatography with electrospray mass spectrometry; Chapter 3: Electrochemical incineration of benzoquinone in aqueous media using a quaternary metal oxide electrode in the absence of a soluble supporting electrolyte; Chapter 4: The determination of electrochemical incineration products of 4-chlorophenol by liquid chromatography-electrospray mass spectrometry; and Chapter 5: Determination of small carboxylic acids by capillary electrophoresis with electrospray mass spectrometry.

  16. Analysis of paralytic shellfish toxins using high-field asymmetric waveform ion mobility spectrometry with liquid chromatography-mass spectrometry.

    PubMed

    Beach, Daniel G; Melanson, Jeremy E; Purves, Randy W

    2015-03-01

    The analysis of paralytic shellfish toxins (PSTs) by liquid chromatography-mass spectrometry remains a challenge because of their high polarity, large number of analogues and the complex matrix in which they occur. Here we investigate the potential utility of high-field asymmetric waveform ion mobility spectrometry (FAIMS) as a gas-phase ion separation tool for analysis of PSTs by mass spectrometry. We investigate the separation of PSTs using FAIMS with two divergent goals: using FAIMS as a primary separation tool for rapid screening by electrospray ionization (ESI)-FAIMS-MS or combined with LC in a multidimensional LC-ESI-FAIMS-MS separation. First, a survey of the parameters that affect the sensitivity and selectivity of PST analysis by FAIMS was carried out using ESI-FAIMS-MS. In particular, the use of acetonitrile as a gas additive in the carrier gas flow offered good separation of all PST epimeric pairs. A second set of FAIMS conditions was also identified, which focussed PSTs to a relatively narrow CV range allowing development of an LC-ESI-FAIMS-MS method for analysis of PST toxins in complex mussel tissue extracts. The quantitative capabilities of this method were evaluated by analysing a PST containing mussel tissue matrix material. Results compared favourably with analysis by an established LC-post-column oxidation-fluorescence method with recoveries ranging from 70 to 106%, although sensitivity was somewhat reduced. The current work represents the first successful separation of PST isomers using ion mobility and shows the promise of FAIMS as a tool for analysis of algal biotoxins in complex samples and outlines some critical requirements for its future improvement. PMID:25619987

  17. Exclusive processes in electron-ion collisions in the dipole formalism

    SciTech Connect

    Cazaroto, E. R.; Navarra, F. S. [Instituto de Fisica, Universidade de Sao Paulo, C.P. 66318, 05314-970 Sao Paulo, SP (Brazil); Carvalho, F. [Departamento de Ciencias Exatas e da Terra, Universidade Federal de Sao Paulo, Campus Diadema, Rua Prof. Artur Riedel, 275, Jd. Eldorado, 09972-270 Diadema, SP (Brazil); Goncalves, V. P. [Instituto de Fisica e Matematica, Universidade Federal de Pelotas, Caixa Postal 354, 96010-900 Pelotas, RS (Brazil)

    2013-03-25

    We compare the predictions of two saturation models for production of vector mesons and of photons in electron-ion collisions. The models considered are the b-CGC and the rcBK. The calculations were made in the kinematical range of the LHeC and of the future eRHIC.

  18. Ion chromatography of organic carboxylic acids. Determination of monobasic carboxylic and hydroxy acids

    SciTech Connect

    Ivanov, A.A.; Shpigun, O.A.; Zolotov, Yu.A.

    1986-07-10

    An ion chromatographic method has been developed for the determination of monobasic carboxylic and hydroxy acids, as well as some of their chloroderivatives. The optimum eluent for the joint determination of monobasic carboxylic and hydroxy acids, fluoride and chloride ions is a 1 x 10/sup -4/ M solution of NaOH. The limit of detection of acids with this eluent is equal to (1.5-3.1) x 10/sup -3/ ..mu..g/ml. Inorganic anions (F/sup -/, Cl/sup -/, NO/sub 3//sup -/, and SO/sub 4//sup 2 -/), as well as dibasic carboxylic and hydroxy acids, do not interfere with the determination of monobasic carboxylic and hydroxy acids. The method has been used for the determination of lactic acid in gastric juice and that of formic, acetic, propionic, and butyric acids in water and condensate of thermoelectric power plants.

  19. Purification of two muscle enzymes by chromatography on immobilized ferric ions.

    PubMed

    Chaga, G; Andersson, L; Ersson, B; Porath, J

    1989-08-01

    Two enzymes, glycogen phosphorylase and lactate dehydrogenase, were purified simultaneously in a single step. Ferric ions immobilized on a chelating gel were used as the adsorbent. Adsorption and desorption steps were accomplished by changes in buffer composition. The recoveries were better than 80% and the capacities were about 5 mg of protein per milliliter of adsorbent. The procedure worked well both on a small and on a preparative scale. The homogeneity of the purified enzymes was checked by FPLC. PMID:2775499

  20. [Analysis of toxaphene and its eight congeners in sediment and fish tissue by gas chromatography-negative ion mass spectrometry].

    PubMed

    Lao, Wenjian

    2013-07-01

    Toxaphene quantification incorporating gas chromatography/negative chemical ionization mass spectrometry (GC/NCI-MS) offers improved sensitivity and specificity. The U. S. Environmental Protection Agency (USEPA) recently released a GC/NCI-MS method (Method 8276) for the measurement of technical toxaphene and eight specific congeners (Hx-Sed, Hp-Sed, P26, P41, P40, P44, P50 and P62). However, there is still lack of a practical and complete analytical method including sample extraction, clean up, instrumental analysis, and data analysis. The goal of this work was to develop a ready-to-use method for the quantification of total toxaphene and the eight congeners. Sediment and salmon fish tissue were selected as sample matrices and extracted with methylene chloride using an accelerated solvent extraction system. The sample extracts were cleaned up with active copper powder or gel permeation chromatography, and finally silica/alumina combination column. Separation was performed on a DB-XLB column. GC/NCI-MS was operated under selected ion monitoring mode with an identical set of confirmation and quantitation ions for total toxaphene and the eight congeners. Oxygen reaction of polychlorinated biphenyls (PCB) was monitored by PCB204, an internal calibration standard, and the reaction level was kept below 1%. Average relative response factors were used in quantitation. Quantitation of total toxaphene employed the sum of all detectable (S/N > or = 3) 6-C1 to 10-Cl homolog peak areas, while the individual congeners were quantified followed the standard procedures for single analytes. Multi-point calibration solutions ranged from 0. 5 (5 for P62) to 500 microg/L for the individual congeners, and 50 to 500 microg/L for technical toxaphene, with the lowest calibration levels as lower limits of quantitation. Average congener recovery was (90.8 +/- 17.4)% (n =10) in spiked sediment with relative standard deviations of 5.4% - 12.8% (n =10), underscoring an excellently accurate and precise method. The method was applied to analyze sediment and fish tissue sample. PMID:24164036

  1. Purification of Soybean Phosphatidylcholine Using D113-III Ion Exchange Macroporous Resin Packed Column Chromatography

    Microsoft Academic Search

    Yuanfa Liu; Liang Shan; Xingguo Wang

    2009-01-01

    Ten ion-exchange resins were compared for their abilities to separate soybean phosphatidylcholine (PC). D113-III resin was\\u000a selected for PC purification among ten resins tested. The optimum PC adsorption conditions were: concentration of PC solution,\\u000a 3 mg\\/mL; pH of PC solution, 7.5; and adsorption flow rate, 1 mL\\/min. The optimum PC desorption conditions were: eluent, 95%\\u000a ethanol aqueous solution; and elution flow rate,

  2. Semiautomated pH gradient ion-exchange chromatography of monoclonal antibody charge variants.

    PubMed

    Talebi, Mohammad; Shellie, Robert A; Hilder, Emily F; Lacher, Nathan A; Haddad, Paul R

    2014-10-01

    A new approach using a chromatography system equipped with isocratic pumps and an electrolytic eluent generator (EG) is introduced, replacing external pH gradient delivery using conventional gradient systems, in which bottled buffers with preadjusted pH are mixed using a gradient pump. The EG is capable of generating high purity base or acid required for online preparation of the buffer at the point of use, utilizing deionized water as the only carrier stream. Typically, the buffer was generated from online titration of a reagent composed of low molecular weight amines. The reagent was delivered isocratically into a static mixing tee, where it was titrated to the required pH with electrolytically generated base or acid. The required pH gradient was thus conveniently generated by electrically controlling the concentration of titrant. Also, since the pH was adjusted at the point of use, this approach offered enhanced throughput in terms of eluent preparation time and labor, and with a more reproducible pH profile. The performance of the system was demonstrated by running pH gradients ranging from pH 8.2 to 10.9 on a polymer monolith cation-exchange column for high throughput profiling of charge heterogeneity of intact, basic therapeutic monoclonal antibodies. A high degree of flexibility in modulating the key parameters of the pH gradient, including the buffer concentration, the pH gradient slope and the operating pH range was demonstrated. This enabled fine-tuning of the separation conditions for each individual antibody in order to enhance the chromatographic resolution. PMID:25199803

  3. Characterization of the chemical constituents in Da-Huang-Gan-Cao-Tang by liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry and liquid chromatography coupled with ion trap mass spectrometry.

    PubMed

    Wang, Shufang; Chen, Pinghong; Xu, Yimin; Li, Xiaodong; Fan, Xiaohui

    2014-07-01

    In this work, the chemical constituents in Da-Huang-Gan-Cao-Tang, a traditional Chinese formula, were studied by liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry and liquid chromatography coupled with ion trap mass spectrometry for the first time. Among the 146 compounds detected in Da-Huang-Gan-Cao-Tang, 104 compounds were identified unambiguously or tentatively based on their accurate molecular weight and multistage MS data, including one potential novel compound and two reported in Glycyrrhiza genus for the first time. The possible fragmentation pathways were proposed and fragmentation rules of the major types of compounds were concluded. This study provided an example to facilitate the tedious identification of chemical composition in traditional Chinese medicine, and maybe a promising reference approach to research the analogous formulae. PMID:24771648

  4. High performance ion chromatography of haloacetic acids on macrocyclic cryptand anion exchanger.

    PubMed

    Bruzzoniti, Maria Concetta; De Carlo, Rosa Maria; Horvath, Krisztian; Perrachon, Daniela; Prelle, Ambra; Tófalvi, Renáta; Sarzanini, Corrado; Hajós, Péter

    2008-04-11

    A new high performance ion chromatographic method has been developed for the separation of the nine chlorinated-brominated haloacetic acids (HAAs) that are the disinfection by-products of chlorination of drinking water, using a macrocycle-based adjustable-capacity anion-exchange separator column (IonPac Cryptand A1). A gradient method based on theoretical and experimental considerations has been optimized in which 10 mM NaOH-LiOH step gradient was performed at the third minute of the analysis. The optimized method allowed us to separate the nine HAAs and seven possibly interfering inorganic anions in less than 25 min with acceptable resolution. The minimum concentrations detectable for HAAs were between 8.0 (MBA) and 210 (TBA) microg L(-1), with linearity included between 0.9947 (TBA) and 0.9998 (MBA). To increase sensitivity, a 25-fold preconcentration step on a reversed phase substrate (LiChrolut EN) has been coupled. Application of this method to the analysis of haloacetic acids in real tap water samples is illustrated. PMID:18304560

  5. Analysis of inorganic nitrogen and related anions in high salinity water using ion chromatography with tandem UV and conductivity detectors.

    PubMed

    Wilson, Brian; Gandhi, Jay; Zhang, Chunlong Carl

    2011-09-01

    Over 97% of the Earth's water is high salinity water in the form of gulfs, oceans, and salt lakes. There is an increasing concern for the quality of water in bays, gulfs, oceans, and other natural waters. These waters are affected by many different sources of contamination. The sources are, but not limited to, groundwater run-off of nitrogen containing fertilizer, pesticides, cleaning agents, solid wastes, industrial waters, and many more. The final destinations of these contaminants are rivers, lakes, and bayous that eventually will lead to bays, gulfs, and oceans. Many industries depend on the quality of these waters, such as the fishing industry. In addition to wild marine life, there are large aquariums and fish and shrimp farms that are required to know the quality of the water. However, the ability of these industries to monitor their processes is limited. Most analytical methods do not apply to the analysis of high salinity waters. They are dependent on wet chemistry techniques, spectrophotometers, and flow analyzers. These methods do not have the accuracy, precision, and sensitivity when compared to ion chromatography (IC). Since the inception of IC, it has become a standard practice for determining the content of many different water samples. Many IC methods are limited in the range of analytes that can be detected, as well as the numerous sample sources of which the methods are applicable. The main focus of current IC methods does not include high salinity waters. This research demonstrates an ion chromatographic method that has the ability to determine low level concentrations of inorganic nitrogen and related anions (nitrite-N, nitrate-N, phosphorous-P, sulfate, bromide, chloride, sulfide, fluoride, ammonia, calcium, and magnesium) in a single run using a combination of UV and conductivity detectors. This method is applicable to various waters, and uses both freshwater and high salinity water samples. PMID:21859532

  6. Determination of nitrosamines in water by gas chromatography/chemical ionization/selective ion trapping mass spectrometry.

    PubMed

    Pozzi, Romina; Bocchini, Paola; Pinelli, Francesca; Galletti, Guido C

    2011-04-01

    A gas chromatography/mass spectrometry (GC/MS) method for determination of nine N-nitrosamines (NAs) in water is described. Two ionization modes, electron impact (EI) and chemical ionization (CI) with methanol, as well as different ion analysis techniques, i.e. full scan, selected ion storage (SIS) and tandem mass spectrometry (MS/MS) were tested. Chemical ionization followed by SIS resulted the mass spectrometric method of choice, with detection limits in the range of 1-2ng/L. Solid Phase Extraction (SPE) with coconut charcoal cartridges was applied to extract NAs from real samples, according EPA Method 521. Drinking water samples were collected from seven surface- and two groundwater treatment plants. Three surface water treatment plants were sampled before and after addition of O(3)/ClO(2) to observe the effect of disinfection on NAs' formation. N-nitrosodiethylamine (NDEA), n-nitrosodipropylamine (NDPA), n-nitrosomorpholine (NMOR) and n-nitrosodibutylamine (NDBA) were found up to concentrations exceeding three times the risk level of 10ng/L set by the California Department of Public Health. Because dermal adsorption has been recently indicated as a new contamination route of exposure to NAs for people who practice swimming activity, water samples from five swimming pools in the Bologna (Italy) area were collected. N-nitrosopyrrolidine (NPYR) was detected in all samples at concentrations larger than 50ng/L, likely as a disinfection by-product from the amino acid precursor proline, a main constituent of skin collagen. PMID:21377686

  7. Use of ion chromatography for the determination of selected metals in blood serum of patients with type 2 diabetes.

    PubMed

    B?azewicz, Anna; Orlicz-Szczesna, Grazyna; Prystupa, Andrzej; Szczesny, Piotr

    2010-01-01

    Ion chromatography followed by microwave-induced acid digestion was used to evaluate the serum levels of Fe(3+), Cu(2+), Ni(2+), Zn(2+), and Mn(2+) in patients with diagnosed type 2 diabetes and in healthy controls. Recoveries ranged from 98.0% to 102% for Fe(3+), from 89.9% to 100% for Cu(2+), from 87.9% to 102% for Zn(2+), and from 89.6% to 102% for Mn(2+) were determined by examining samples spiked with various amounts of all the studied ions. The time of mineralization longer than 28 min did not affect the assay values. Precision was assessed at four unique concentrations in replicates of six, on four separate occasions. RSD was determined to be 1.16% for Fe(3+), 5.20% for Cu(2+), 2.8% for Zn(2+), and 3.75% for Mn(2+). The accuracy results (values of RSD) were as follows: 5.16% for Fe(3+), 6.35% for Cu(2+), 4.9% for Zn(2+), and 7.23% for Mn(2+). The statistical analysis confirmed that mean concentrations of Fe(3+) and Zn(2+) did not differ significantly from analogous values in the control group. Patients who additionally suffered from hypertension had higher copper concentrations compared with diabetic patients. For diabetics the presence of Mn(2+) was not stated (LOD values amounting to 0.006 microg/mL). Ni(2+) was not detectable for either the studied group or the control group (LOD=0.006 microg/mL). PMID:20122574

  8. Potential of ion chromatography coupled to isotope ratio mass spectrometry via a liquid interface for beverages authentication.

    PubMed

    Guyon, Francois; Gaillard, Laetitia; Brault, Audrey; Gaultier, Nicolas; Salagoïty, Marie-Hélène; Médina, Bernard

    2013-12-27

    New tools for the determination of characteristic parameters for food authentication are requested to prevent food adulteration from which health concerns, unfair competition could follow. A new coupling in the area of compound-specific carbon 13 isotope ratio (?(13)C) analysis was developed to simultaneously quantify ?(13)C values of sugars and organic acids. The coupling of ion chromatography (IC) together with isotope ratio mass spectrometry (IRMS) can be achieved using a liquid interface allowing a chemical oxidation (co) of organic matter. Synthetic solutions containing 1 polyol (glycerol), 3 carbohydrates (sucrose, glucose and fructose) and 12 organic acids (gluconic, lactic, malic, tartaric, oxalic, fumaric, citric and isocitric) were used to optimize chromatographic conditions (concentration gradient and 3 types of column) and the studied isotopic range (-32.28 to -10.65‰) corresponds to the values found in food products. Optimum chromatographic conditions are found using an IonPac AS15, an elution flow rate of 0.3mLmin(-1) and a linear concentration gradient from 2 to 76mM (rate 21mMmin(-1)). Comparison between ?(13)C value individually obtained for each compound with the coupling IRMS and elemental analyzer, EA-IRMS, and the ones measured on the mixture of compounds by IC-co-IRMS does not reveal any isotope fractionation. Thus, under these experimental conditions, IC-co-IRMS results are accurate and reproducible. This new coupling was tested on two food matrices, an orange juice and a sweet wine. Some optimization is necessary as the concentration range between sugars and organic acids is too large: an increase in the filament intensity of the IRMS is necessary to simultaneously detect the two compound families. These first attempts confirm the good results obtained on synthetic solutions and the strong potential of the coupling IC-co-IRMS in food authentication area. PMID:24267317

  9. Isolation and mass spectrometry characterization of molecular species of lactosylceramides using liquid chromatography-electrospray ion trap mass spectrometry.

    PubMed

    Kaga, Naoko; Kazuno, Saiko; Taka, Hikari; Iwabuchi, Kazuhisa; Murayama, Kimie

    2005-02-15

    Reverse-phase liquid chromatography/electrospray ion trap mass spectrometry (LC-ESI-MSn) was established for identification of the molecular species of lactosylceramides. Lactosylceramides derived from porcine blood cells were separated on a CapcellPak C8 column using a mixture of methanol and 1 mM ammonium formate from the C16 to C26 fatty acyl chains based on the length of total carbon chains and the nature of sphingoid bases (w'') and fatty acyl chains (Y0'-w'') was identified by MS3 as their [M+H]+ ions. The same number of fatty acyl moieties appeared in the order of unsaturated, (2-)hydroxylated, and saturated components. The molecular species of lactosylceramides derived from porcine blood cells totaled more than 33 and included mainly C24:0-d18:1, Ch24:0-d18:1, Ch24:1-d18:1, C24:1-d18:1, and C22:0-d18:1 in addition to 28 minor species from C16:0 to C26:0 fatty acyl moieties. The molecular species of lactosylceramides in the membrane microdomain fraction of HL-60 cells (70% were differentiated into macrophage-lineage cells) were identified as C24:0-d18:1, C24:1-d18:1, C22:0-d18:1, C16:0-d18:1, and more than 21 other minor species. Our results suggest that reverse-phase LC-ESI-MSn is a useful and simple method for identification of lactosylceramide molecular species. PMID:15691512

  10. Retention behavior of o-phthalic, 3-nitrophthalic, and 4-nitrophthalic acids in ion-suppression reversed-phase high performance liquid chromatography using acids instead of buffers as ion-suppressors.

    PubMed

    Lian, Hong-Zhen; Wang, Wei-Han; Li, Dan-Ni

    2005-07-01

    In reversed-phase high performance liquid chromatography, the logarithm of the retention factor, log k, is usually correlated with the logarithm of the octanol-water partition coefficient, log Kow. The k and Kow of an ionizable analyte are greatly influenced by the mobile phase pH. In this paper, log kw of diprotic o-phthalic, 3-nitrophthalic, and 4-nitrophthalic acids, are obtained by extrapolation to pure aqueous fraction of mobile phase in ion-suppression reversed-phase high performance liquid chromatography with acetic acid and perchloric acid as the ion-suppressors. The Kow values of the three analytes are calibrated according to the apparent octanol-water partition coefficient, Kow, under different pH conditions, and the log K"ow values show a much better correlation with log kw than do log Kow. The influences of two ion-suppressors, acetic and perchloric acids, on the retention behavior of these diprotic acids at different pH are contrasted. An abnormal trend is found in the k vs. pHw plot of the acetic acid system when the methanol content is low. A possible reason is that acetic acid is an even stronger organic modifier than methanol, besides being an ion-suppressor. The results make the selection of mobile phase for the separation of acidic compounds by ion-suppression reversed-phase high performance liquid chromatography direct, accurate, and practical. PMID:16116995

  11. Analysis of atmospheric aerosols by particle-induced X-ray emission, instrumental neutron activation analysis, and ion chromatography

    NASA Astrophysics Data System (ADS)

    Maenhaut, Willy; Raes, Nico; Wang, Wan

    2011-11-01

    Particle-induced X-ray emission (PIXE), ion chromatography (IC), and occasionally also instrumental neutron activation analysis (INAA) were used in combination for the analysis of atmospheric aerosol samples that were collected on Nuclepore polycarbonate filters. A comparison of the results enabled us to evaluate the matrix effects (i.e., particle size effects) of the PIXE analysis for the light elements and to assess the water-solubility and/or speciation of a number of elements (e.g., S, K, Ca). Results are presented from several measurement campaigns at urban and forested sites in Europe, whereby PM10 or PM2.5 filter samples were taken. From the PIXE and IC results for a 2003 summer campaign at the K-puszta site in Hungary, it was estimated that organosulphates could be responsible for 20% of the total sulphur concentration and 30% of the organic aerosol in PM10. The comparison of the IC and PIXE data for K and Ca from the various sites indicated that most of the Ca was water-soluble (the mineral dust Ca was presumably mostly present as calcite, and perhaps also in part as gypsum); in contrast, for K, only half of it was typically water-soluble, indicating that it was to a large extent associated with insoluble mineral dust. Exceptions, with almost fully water-soluble K, were found for samples that were substantially impacted by biomass burning.

  12. Quantification of paraquat in postmortem samples by gas chromatography-ion trap mass spectrometry and review of the literature.

    PubMed

    Moreira, Pedro Nuno; de Pinho, Paula Guedes; Baltazar, Maria Teresa; Bastos, Maria Lourdes; Carvalho, Félix; Dinis-Oliveira, Ricardo Jorge

    2012-03-01

    Paraquat (PQ) is an herbicide implicated in numerous fatalities, mainly caused by voluntary ingestion. Several methods have been used to quantify PQ in plasma and urine samples of intoxicated humans as a predictor of clinical outcome. There is no validated method for the analysis of PQ in postmortem samples. Therefore, the aim of this study was to develop an analytical method, using gas chromatography-ion trap mass spectrometry (GC-IT/MS) after solid-phase extraction, to quantify PQ in postmortem samples, namely in whole blood, urine, liver, lung and kidney, to cover the routes of distribution, accumulation and elimination of PQ. The method proved to be selective as there were no interferences of endogenous compounds with the same retention time as PQ and ethyl paraquat (internal standard). The regression analysis for PQ was linear in the range 0-10?µg/mL. The detection limits ranged from 0.0076?µg/mL for urine to 0.047?µg/mL for whole blood, and the recoveries were suitable for forensic analysis. The proposed GC-IT/MS method provided an accurate and simple assay with adequate precision and recovery for the quantification of PQ in postmortem samples. The proof of applicability was performed in two fatal PQ intoxications. A review of the analytical methods for the determination of quaternary ammonium herbicides is also provided for a better understanding of the presently available techniques. PMID:21656535

  13. Determination of arsenic speciation in sulfidic waters by Ion Chromatography Hydride-Generation Atomic Fluorescence Spectrometry (IC-HG-AFS).

    PubMed

    Keller, Nicole S; Stefánsson, Andri; Sigfússon, Bergur

    2014-10-01

    A method for the analysis of arsenic species in aqueous sulfide samples is presented. The method uses an ion chromatography system connected with a Hydride-Generation Atomic Fluorescence Spectrometer (IC-HG-AFS). With this method inorganic As(III) and As(V) species in water samples can be analyzed, including arsenite (HnAs(III)O3(n-3)), thioarsenite (HnAs(III)S3(n-3)), arsenate (HnAs(V)O4(n-3)), monothioarsenate (HnAs(V)SO3(n-3)), dithioarsenate (HnAs(V)S2O2(n-3)), trithioarsenate (HnAs(V)S3O(n-3)) and tetrathioarsenate (HnAs(V)S4(n-3)). The peak identification and retention times were determined based on standard analysis of the various arsenic compounds. The analytical detection limit was ~1-3 µg L(-1) (LOD), depending on the quality of the baseline. This low detection limit makes this method also applicable to discriminate between waters meeting the drinking water standard of max. 10 µg L(-1) As, and waters that do not meet this standard. The new method was successfully applied for on-site determination of arsenic species in natural sulfidic waters, in which seven species were unambiguously identified. PMID:25059187

  14. Derivatization Ion Chromatography for the Determination of Monoethanolamine in Presence of Hydrazine in PHWR Steam-Water Circuits

    PubMed Central

    D., Ayushi; Sengupta, Arijit; Kumar, Sangita D.; Kumbhar, A. G.; Venkateswaran, G.

    2011-01-01

    A simple, rapid and accurate method for the determination of monoethanolamine (MEA) in PHWR steam-water circuits has been developed. MEA is added in the feed water to provide protection against corrosion while hydrazine is added to scavenge dissolved oxygen. The quantitative determination of MEA in presence of hydrazine was accomplished using derivatization ion chromatography with conductometric detection in nonsuppressed mode. A Metrosep cation 1-2 analytical column and a Metrosep cartridge were used for cation separation. A mixture of 4?mM tartaric acid, 20% acetone and 0.05?mM HNO3 was used as eluent. Acetone in the mobile phase leads to the formation of different derivatives with MEA and hydrazine. The interferences due Na+ and NH4?+ were eliminated by adopting a simple pretreatment procedure employing OnGuard-H cartridge. The limit of detection limit of MEA was 0.1??g?mL?1 and the relative standard deviation was 2% for the overall method. The recovery of MEA added was in the range 95%–102%. The method was applied to the determination of MEA in steam generator water samples. PMID:21785596

  15. Optimization of Immobilized Gallium (III) Ion Affinity Chromatography for Selective Binding and Recovery of Phosphopeptides from Protein Digests

    PubMed Central

    Aryal, Uma K.; Olson, Douglas J.H.; Ross, Andrew R.S.

    2008-01-01

    Although widely used in proteomics research for the selective enrichment of phosphopeptides from protein digests, immobilized metal-ion affinity chromatography (IMAC) often suffers from low specificity and differential recovery of peptides carrying different numbers of phosphate groups. By systematically evaluating and optimizing different loading, washing, and elution conditions, we have developed an efficient and highly selective procedure for the enrichment of phosphopeptides using a commercially available gallium(III)-IMAC column (PhosphoProfile, Sigma). Phosphopeptide enrichment using the reagents supplied with the column is incomplete and biased toward the recovery and/or detection of smaller, singly phosphorylated peptides. In contrast, elution with base (0.4 M ammonium hydroxide) gives efficient and balanced recovery of both singly and multiply phosphorylated peptides, while loading peptides in a strong acidic solution (1% trifluoracetic acid) further increases selectivity toward phosphopeptides, with minimal carryover of nonphosphorylated peptides. 2,5-Dihydroxybenzoic acid, a matrix commonly used when analyzing phosphopeptides by matrix-assisted laser desorption/ionization mass spectrometry was also evaluated as an additive in loading and eluting solvents. Elution with 50% acetonitrile containing 20 mg/mL dihydroxybenzoic acid and 1% phosphoric acid gave results similar to those obtained using ammonium hydroxide as the eluent, although the latter showed the highest specificity for phosphorylated peptides. PMID:19183793

  16. Optimization of immobilized gallium (III) ion affinity chromatography for selective binding and recovery of phosphopeptides from protein digests.

    PubMed

    Aryal, Uma K; Olson, Douglas J H; Ross, Andrew R S

    2008-12-01

    Although widely used in proteomics research for the selective enrichment of phosphopeptides from protein digests, immobilized metal-ion affinity chromatography (IMAC) often suffers from low specificity and differential recovery of peptides carrying different numbers of phosphate groups. By systematically evaluating and optimizing different loading, washing, and elution conditions, we have developed an efficient and highly selective procedure for the enrichment of phosphopeptides using a commercially available gallium(III)-IMAC column (PhosphoProfile, Sigma). Phosphopeptide enrichment using the reagents supplied with the column is incomplete and biased toward the recovery and/or detection of smaller, singly phosphorylated peptides. In contrast, elution with base (0.4 M ammonium hydroxide) gives efficient and balanced recovery of both singly and multiply phosphorylated peptides, while loading peptides in a strong acidic solution (1% trifluoracetic acid) further increases selectivity toward phosphopeptides, with minimal carryover of nonphosphorylated peptides. 2,5-Dihydroxybenzoic acid, a matrix commonly used when analyzing phosphopeptides by matrix-assisted laser desorption/ionization mass spectrometry was also evaluated as an additive in loading and eluting solvents. Elution with 50% acetonitrile containing 20 mg/mL dihydroxybenzoic acid and 1% phosphoric acid gave results similar to those obtained using ammonium hydroxide as the eluent, although the latter showed the highest specificity for phosphorylated peptides. PMID:19183793

  17. [Determination of short chain chlorinated paraffins in polyvinyl chloride plastics by gas chromatography-negative chemical ion/mass spectrometry].

    PubMed

    Xing, Yuanna; Lin, Zhihui; Feng, Anhong; Wang, Xin; Gong, Yemeng; Chen, Zeyong

    2015-02-01

    A novel method was established to determine short chain chlorinated paraffins (SC-CPs) in polyvinyl chloride (PVC) plastics by gas chromatography-negative chemical ion/mass spectrometry (GC-NCI/MS). Ultrasonic extraction was used to extract SCCPs from PVC plastics. The optimal extraction time was 1.5 h, and concentrated sulfuric acid was adopted to purify the extracted solution. Finally, SCCPs in a sample were detected by GC-NCI/MS at 160 C and with methane reagent gas at 1. 5 mL/min. This method was not influenced by medium chain chlorinated paraffins (MCCPs) in the sample, and accurate quantitation was made for SCCPs. Twelve batches of samples were analyzed and SCCPs were detected in each batch with the contents from 0. 3 x 10(2)mg/kg to 3. 5 x 10(4)mg/kg. With respect to European limitation of SC-CPs (1%), four batches of samples did not comply with the European regulation, and they accounted for 33. 3%. Obviously, high SCCPs risk was presented in PVC plastics. PMID:25989692

  18. Strategies for the analysis of chlorobenzenes in soils using solid-phase microextraction coupled with gas chromatography–ion trap mass spectrometry

    Microsoft Academic Search

    M. N Sarrión; F. J Santos; M. T Galceran

    1998-01-01

    Solid-phase microextraction (SPME) was examined as a possible alternative to Soxhlet extraction in the analysis of chlorobenzenes at high concentrations (up to 65 ?gg?1) in soils. Gas chromatography–ion trap mass spectrometry (GC–IT-MS) was used and different strategies were tested in order to obtain suitable responses for chlorobenzenes. Two headspace SPME methods, using fibres coated with polydimethylsiloxane (PDMS) as stationary phase,

  19. Determination of trace concentrations of bromate in municipal and bottled drinking waters using a hydroxide-selective column with ion chromatography

    Microsoft Academic Search

    Brian M. De Borba; Jeff S. Rohrer; Chris A. Pohl; Charanjit Saini

    2005-01-01

    The International Agency for Research on Cancer determined that bromate is a potential human carcinogen, even at low ?g\\/l levels in drinking water. Bromate is commonly produced from the ozonation of source water containing naturally occurring bromide. Traditionally, trace concentrations of bromate and other oxyhalides in environmental waters have been determined by anion exchange chromatography with an IonPac AS9-HC column

  20. Quantitative analysis in gas chromatography\\/low power atmospheric-pressure helium microwave-induced plasma atomic emission interferometry and ion cyclotron resonance mass spectroscopy

    Microsoft Academic Search

    Loo

    1990-01-01

    The development of experimental and data analysis techniques for quantitative analysis in gas chromatography\\/low power atmospheric pressure helium microwave-induced plasma atomic emission interferometry (GC\\/HeMIPAEI) and ion cyclotron resonance mass spectroscopy (ICR\\/MS) is presented. A discussion of interferometric data analysis by discrete and fast Fourier transform (DFT and FFT, respectively) is given. Additionally, the use of two techniques (the maximum entropy

  1. Stability studies of propoxur herbicide in environmental water samples by liquid chromatography–atmospheric pressure chemical ionization ion-trap mass spectrometry

    Microsoft Academic Search

    Lei Sun; Hian Kee Lee

    2003-01-01

    Liquid chromatography–atmospheric pressure ionization ion-trap mass spectrometry has been investigated for the analysis of polar pesticides in water. The degradation behavior of propoxur, selected as a model pesticide belonging to the N-methylcarbamate group, in various aqueous matrices (Milli-Q water, drinking water, rain water, seawater and river water) was investigated. Two interfaces of atmospheric pressure ionization, atmospheric pressure chemical ionization (APCI)

  2. Determination of nitrated polycyclic aromatic hydrocarbons in diesel particulate-related standard reference materials by using gas chromatography\\/mass spectrometry with negative ion chemical ionization

    Microsoft Academic Search

    Dawit Z. Bezabeh; Holly A. Bamford; Michele M. Schantz; Stephen A. Wise

    2003-01-01

    Gas chromatography\\/mass spectrometry (GC\\/MS) with negative ion chemical ionization (NICI) detection was utilized for quantitative determination of nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) in diesel particulate-related standard reference materials (SRMs). Prior to GC\\/MS analysis, isolation of the nitro-PAHs from the complex diesel particulate extract was accomplished using solid phase extraction (SPE) and normal-phase liquid chromatographic (LC) fractionation using an amino\\/cyano stationary

  3. Trace analysis of heavy metals in groundwater samples by ion chromatography with post-column reaction and ultraviolet–visible detection

    Microsoft Academic Search

    E Santoyo; S Santoyo-Gutiérrez; Surendra P Verma

    2000-01-01

    Groundwaters originating from local and regional aquifers surrounding ash deposits produced by a coal-fired power plant were collected. These water samples were chemically analyzed for quantifying their heavy metal composition at trace levels. A highly sensitive analytical technique based on ion chromatography with a UV–Vis detector and under isocratic eluent flow-rate conditions was used. In order to quantify the major

  4. Identification and Quantification of 8 Sulfonylureas with Clinical Toxicology Interest by Liquid Chromatography-Ion-Trap Tandem Mass Spectrometry and Library Searching

    Microsoft Academic Search

    Guillaume Hoizey; Denis Lamiable; Thierry Trenque; Arnaud Robinet; Laurent Binet; Matthieu L. Kaltenbach; Sandrine Havet

    Background: Identification of sulfonylureas in blood may be useful in the evaluation of hypoglycemic crises of unknown origin. The aim of the present study was to develop a highly selective liquid chromatography-elec- trospray tandem mass spectrometry (MS-MS) method using an ion-trap detector for rapid screening, identifi- cation, and quantification of sulfonylureas in human plasma. Methods: After standard liquid-liquid extraction with

  5. Target-guided separation of Bougainvillea glabra betacyanins by direct coupling of preparative ion-pair high-speed countercurrent chromatography and electrospray ionization mass-spectrometry

    Microsoft Academic Search

    Gerold Jerz; S?awomir Wybraniec; Nadine Gebers; Peter Winterhalter

    2010-01-01

    In this study, preparative ion-pair high-speed countercurrent chromatography was directly coupled to an electrospray ionization mass-spectrometry device (IP-HSCCC\\/ESI-MS-MS) for target-guided fractionation of high molecular weight acyl-oligosaccharide linked betacyanins from purple bracts of Bougainvillea glabra (Nyctaginaceae). The direct identification of six principal acyl-oligosaccharide linked betacyanins in the mass range between m\\/z 859 and m\\/z 1359 was achieved by positive ESI-MS ionization

  6. Determination of haloacetic acids in aqueous environments by solid-phase extraction followed by ion-pair liquid chromatography–electrospray ionization mass spectrometric detection

    Microsoft Academic Search

    Robert Loos; Damià Barceló

    2001-01-01

    Haloacetic acids (HAAs) were determined in different water samples by a new, fast and simple analysis method based on enrichment of 50-ml water samples at pH 1.8 by solid-phase extraction (SPE) followed by liquid chromatography (LC) separation and electrospray ionization mass spectrometric detection in the negative ionization mode. Deprotonated (M-H)? haloacetates and decarboxylated (M-COOH)? ions were detected. Different polymeric SPE

  7. Diffusion scrubber-ion chromatography for the measurement of trace levels of atmospheric HCl

    NASA Astrophysics Data System (ADS)

    Lindgren, Per F.

    A diffusion scrubber-ion chromatographic (DS-IC) instrument has been characterized and employed for the measurement of trace levels of gaseous HCl in the atmosphere. The instrument operates with a temporal resolution of 5 min and the detection limit is estimated to be 5 pptv. Collection efficiencies for HCl with two identical diffusion scrubbers were 28±2% and 20±2%, respectively, at a sampling flow rate of 2 SLPM. Instrument response decreases with increased relative humidity. An equation, correction factor=2.45 × 10 -7 × %r.h 3 + 1.00, is used to correct for the relative humidity dependency. The instrument was tested in ambient air studies by measuring background mixing ratios between 0.02 and 0.5 ppbv at a suburban sampling site. Calibration of the instrument was carried out with a novel source of gaseous HCl based on sublimation of ammonium chloride.

  8. Comparison of Gas Chromatography-Mass Spectrometry and Gas Chromatography-Tandem Mass Spectrometry with Electron Ionization and Negative-Ion Chemical Ionization for Analyses of Pesticides at Trace Levels in Atmospheric Samples

    PubMed Central

    Raina, Renata; Hall, Patricia

    2008-01-01

    A comparison of detection limits of gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) with gas chromatography-tandem mass spectrometry (GC-MS/MS) in selected reaction monitoring (SRM) mode with both electron ionization (EI) and negative-ion chemical ionization (NCI) are presented for over 50 pesticides ranging from organochlorines (OCs), organophosphorus pesticides (OPs) and pre-emergent herbicides used in the Canadian prairies (triallate, trifluralin, ethalfluralin). The developed GC-EI/SIM, GC-NCI/SIM, and GC-NCI/SRM are suitable for the determination of pesticides in air sample extracts at concentrations <100 pg ?L?1 (<100 pg m?3 in air). No one method could be used to analyze the range of pre-emergent herbicides, OPs, and OCs investigated. In general GC-NCI/SIM provided the lowest method detection limits (MDLs commonly 2.5–10 pg ?L?1) along with best confirmation (<25% RSD of ion ratio), while GC-NCI/SRM is recommended for use where added selectivity or confirmation is required (such as parathion-ethyl, tokuthion, carbofenothion). GC-EI/SRM at concentration <100 pg ?L?1 was not suitable for most pesticides. GC-EI/SIM was more prone to interference issues than NCI methods, but gave good sensitivity (MDLs 1–10 pg ?L?1) for pesticides with poor NCI response (OPs: sulfotep, phorate, aspon, ethion, and OCs: alachlor, aldrin, perthane, and DDE, DDD, DDT). PMID:19609395

  9. Fragmentation of toxicologically relevant drugs in positive-ion liquid chromatography-tandem mass spectrometry.

    PubMed

    Niessen, W M A

    2011-01-01

    The identification of drugs and related compounds by LC-MS-MS is an important analytical challenge in several application areas, including clinical and forensic toxicology, doping control analysis, and environmental analysis. Although target-compound based analytical strategies are most frequently applied, at some point the information content of the MS-MS spectra becomes relevant. In this article, the positive-ion MS-MS spectra of a wide variety of drugs and related substances are discussed. Starting point was an MS-MS mass spectral library of toxicologically relevant compounds, available on the internet. The positive-ion MS-MS spectra of ?570 compounds were interpreted by chemical and therapeutic class, thus involving a wide variety of drug compound classes, such benzodiazepines, beta-blockers, angiotensin-converting enzyme inhibitors, phenothiazines, dihydropyridine calcium channel blockers, diuretics, local anesthetics, vasodilators, as well as various subclasses of anti-diabetic, antidepressant, analgesic, and antihistaminic drugs. In addition, the scientific literature was searched for available MS-MS data of these compound classes and the interpretation thereof. The results of this elaborate study are presented in this article. For each individual compound class, the emphasis is on class-specific fragmentation, as discussing fragmentation of all individual compounds would take far too much space. The recognition of class-specific fragmentation may be quite informative in determining the compound class of a specific unknown, which may further help in the identification. In addition, knowledge on (class-specific) fragmentation may further help in the optimization of the selectivity in targeted analytical approaches of compounds of one particular class. PMID:21294151

  10. Analysis of anions in aqueous samples by ion chromatography and capillary electrophoresis. A comparative study of peak modeling and validation criteria.

    PubMed

    Tamisier-Karolak, S L; Le Potier, I; Barlet, O; Czok, M

    1999-08-13

    The object of this study is the comparison of two methods for the quantitative analysis of anions in aqueous samples: ion chromatography with conductimetric detection, and capillary zone electrophoresis with indirect photometric detection. The comparison includes modeling of experimental peaks as well as statistical validation criteria according to the recommendations of the International Conference on Harmonisation. In ion chromatography, peak shapes are Gaussian or exponentially modified Gaussian, and the number of theoretical plates calculated using the appropriate mathematical relations correspond well to those obtained from statistical moments. Peaks in capillary electrophoresis, however, do not follow the same models. A different model, treating the peaks as right angle triangles, has been studied. Equations corresponding to this model permit a good estimation of plate numbers. The statistical validation of these methods includes detection limits, linearity, accuracy and precision. Overall, ion chromatography yields better validation results than capillary electrophoresis. In the latter method the injection mode plays an important role, with voltage injection giving lower detection limits than hydrodynamic injection. PMID:10481986

  11. Measurement of gas-phase ammonia and amines in air by collection onto an ion exchange resin and analysis by ion chromatography

    NASA Astrophysics Data System (ADS)

    Dawson, M. L.; Perraud, V.; Gomez, A.; Arquero, K. D.; Ezell, M. J.; Finlayson-Pitts, B. J.

    2014-02-01

    Ammonia and amines are common trace gases in the atmosphere and have a variety of both biogenic and anthropogenic sources, with a major contribution coming from agricultural sites. In addition to their malodorous nature, both ammonia and amines have been shown to enhance particle formation from acids such as nitric, sulfuric and methanesulfonic acids, which has implications for visibility, human health and climate. A key component of quantifying the effects of these species on particle formation is accurate gas-phase measurements in both laboratory and field studies. However, these species are notoriously difficult to measure as they are readily taken up on surfaces, including onto glass surfaces from aqueous solution as established in the present studies. We describe here a novel technique for measuring gas-phase ammonia and amines that involves uptake onto a weak cation exchange resin followed by extraction and analysis using ion chromatography. Two variants, one for ppb concentrations in air and the second with lower (ppt) detection limits, are described. The latter involves the use of a custom-designed high-pressure cartridge to hold the resin for in-line extraction. These methods avoid the use of sampling lines, which can lead to significant inlet losses of these compounds. They also have the advantages of being relatively simple and inexpensive. The applicability of this technique to ambient air is demonstrated in measurements made near a cattle farm in Chino, CA.

  12. Measurement of gas-phase ammonia and amines in air by collection onto an ion exchange resin and analysis by ion chromatography

    NASA Astrophysics Data System (ADS)

    Dawson, M. L.; Perraud, V.; Gomez, A.; Arquero, K. D.; Ezell, M. J.; Finlayson-Pitts, B. J.

    2014-08-01

    Ammonia and amines are common trace gases in the atmosphere and have a variety of both biogenic and anthropogenic sources, with a major contribution coming from agricultural sites. In addition to their malodorous nature, both ammonia and amines have been shown to enhance particle formation from acids such as nitric, sulfuric and methanesulfonic acids, which has implications for visibility, human health and climate. A key component of quantifying the effects of these species on particle formation is accurate gas-phase measurements in both laboratory and field studies. However, these species are notoriously difficult to measure as they are readily taken up on surfaces, including onto glass surfaces from aqueous solution as established in the present studies. We describe here a novel technique for measuring gas-phase ammonia and amines that involves uptake onto a weak cation exchange resin followed by extraction and analysis using ion chromatography. Two variants - one for parts per billion concentrations in air and the second with lower (parts per trillion) detection limits - are described. The latter involves the use of a custom-designed high-pressure cartridge to hold the resin for in-line extraction. These methods avoid the use of sampling lines, which can lead to significant inlet losses of these compounds. They also have the advantages of being relatively simple and inexpensive. The applicability of this technique to ambient air is demonstrated in measurements made near a cattle farm in Chino, CA.

  13. Modeling of salt and pH gradient elution in ion-exchange chromatography.

    PubMed

    Schmidt, Michael; Hafner, Mathias; Frech, Christian

    2014-01-01

    The separation of proteins by internally and externally generated pH gradients in chromatofocusing on ion-exchange columns is a well-established analytical method with a large number of applications. In this work, a stoichiometric displacement model was used to describe the retention behavior of lysozyme on SP Sepharose FF and a monoclonal antibody on Fractogel SO3 (S) in linear salt and pH gradient elution. The pH dependence of the binding charge B in the linear gradient elution model is introduced using a protein net charge model, while the pH dependence of the equilibrium constant is based on a thermodynamic approach. The model parameter and pH dependences are calculated from linear salt gradient elutions at different pH values as well as from linear pH gradient elutions at different fixed salt concentrations. The application of the model for the well-characterized protein lysozyme resulted in almost identical model parameters based on either linear salt or pH gradient elution data. For the antibody, only the approach based on linear pH gradients is feasible because of the limited pH range useful for salt gradient elution. The application of the model for the separation of an acid variant of the antibody from the major monomeric form is discussed. PMID:24415551

  14. The mechanism for the exclusion of sugars from the water in a model of the liveing cell: the ion-exchange resin: pore size or water structure?

    PubMed

    Ling, G N; Sobel, A M

    1975-01-01

    The equilibrium distribution coefficients (p-value) of D-arabinose between the water in sulfonate ion-exchange resin and the external aqueous solution vary with the nature of the five alkali metal counterions studied. The strongest exclusion (lowest p-value) is found in the Li+ resin and the least exclusion (highest p-value) in the Cs+ resin. The p-value decreases with the increasing atomic weights for the alkali-metal ions: pCs+ greater than or equal to pRb+ greater than or equal to pRb+ greater than or equal to pK+ greater than pNa+ greater than pLi+. The water contents of these resins, on the other hand, vary in the opposite direction, being highest for the Li+ resin and lowest for the Cs+ resin. These data disprove the pore size theory but fully substantiate the predictions of the association-induction hypothesis. PMID:1197383

  15. Liquid chromatography coupled to negative electrospray/ion trap mass spectrometry for the identification of isomeric glutathione conjugates of catechol estrogens

    NASA Astrophysics Data System (ADS)

    Rathahao, E.; Page, A.; Jouanin, I.; Paris, A.; Debrauwer, L.

    2004-02-01

    Conjugation to glutathione (GSH) represents an important detoxification pathway for preventing DNA damage due to oxidation products of catechol estrogens. In order to identify isomeric GSH conjugates of catechol estrogens, liquid chromatography coupled to electrospray/ion trap mass spectrometry was used. For this purpose, both positive and negative ion modes were applied, generating protonated and deprotonated species, respectively. Energy-resolved fragmentation of each isomeric quasi-molecular ion was achieved in two regions of the mass spectrometer: (i) the mass analyzer (ion trap mass spectrometer) and (ii) the interface region of the electrospray ionization source. The resonance excitation of [M+H]+ protonated ions carried out into the ion trap did not show any isomeric differentiation. Although ion source fragmentation of these same species allowed identification of each isomer, this method requires a good chromatographic separation, making it inefficient for the analysis of low sample amounts from in vitro or in vivo sources. Conversely, using resonance excitation of deprotonated ions, isomer distinction could be achieved. Thus, this technique should yield the best data for the direct characterization of isomers of catechol estrogen-GSH conjugates from biological samples.

  16. Ion exchange chromatography of proteins-predictions of elution curves and operating conditions. II. Experimental verification.

    PubMed

    Yamamoto, S; Nakanishi, K; Matsuno, R; Kamijubo, T

    1983-05-01

    The applicability and validity of the model developed in Part I were confirmed experimentally. In this article, various proteins were eluted both by stepwise and linear gradient elution on DEAE ion exchangers under a variety of experimental conditions. Adsorption isotherms were measured as a function of ionic strength in batch experiments. The moment method was employed for the determination of various parameters such as the gel-phase diffusion coefficient and the longitudinal dispersion coefficient. By use of these parameters and the experimentally measured ionic strength of the peak position, the number of plates was determined according to the method described in Part I. Theoretical elution curves were calculated with the experimentally measured adsorption equilibria and the number of plates. Good agreement was observed between theory an experiments. Various factors affecting the separation were investigated. It was found that the effect of the number of plates for salts, N'(p), was negligible except the case of stepwise elution of high ionic strength buffer. When elution curves were symmetrical, the widths of the elution curves were inversely proportional to the square root of the number of plates of proteins, N(p), as in other chromatographic techniques. A simple graphical method for prediction of the peak position in linear gradient elution described in Part I was found applicable when the elution curves were symmetrical. A useful correlation of prediction of the peak width in a linear gradient elution was proposed on the basis of the approximate solution derived in Part I of this study. This graphical method and correlation permit easy prediction of the peak position and peak width in linear gradient elution in the case of symmetrical elution curves. PMID:18548766

  17. Ultrafiltration by a compacted clay membrane-II. Sodium ion exclusion at various ionic strengths

    USGS Publications Warehouse

    Hanshaw, B.B.; Coplen, T.B.

    1973-01-01

    Several recent laboratory studies and field investigations have indicated that shales and compacted clay minerals behave as semipermeable membranes. One of the properties of semipermeable membranes is to retard or prevent the passage of charged ionic species through the membrane pores while allowing relatively free movement of uncharged species. This phenomenon is termed salt filtering, reverse osmosis, or ultrafiltration. This paper shows how one can proceed from the ion exchange capacity of clay minerals and, by means of Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane. Reasonable agreement between theory and laboratory results were found. The concentration of the ultrafiltrate was always greater than predicted because of uncertainty in values of some parameters in the equations. Ultrafiltration phenomena may be responsible for the formation of some subsurface brines and mineral deposits. The effect should also be taken into consideration in any proposal for subsurface waste emplacement in an environment containing large quantities of clay minerals. ?? 1973.

  18. Qualitative and Quantitative Characterization of Plasma Proteins When Incorporating Traveling Wave Ion Mobility into a Liquid Chromatography–Mass Spectrometry Workflow for Biomarker Discovery: Use of Product Ion Quantitation As an Alternative Data Analysis Tool for Label Free Quantitation

    PubMed Central

    2014-01-01

    Discovery of protein biomarkers in clinical samples necessitates significant prefractionation prior to liquid chromatography–mass spectrometry (LC–MS) analysis. Integrating traveling wave ion mobility spectrometry (TWIMS) enables in-line gas phase separation which when coupled with nanoflow liquid chromatography and data independent acquisition tandem mass spectrometry, confers significant advantages to the discovery of protein biomarkers by improving separation and inherent sensitivity. Incorporation of TWIMS leads to a packet of concentrated ions which ultimately provides a significant improvement in sensitivity. As a consequence of ion packeting, when present at high concentrations, accurate quantitation of proteins can be affected due to detector saturation effects. Human plasma was analyzed in triplicate using liquid-chromatography data independent acquisition mass spectrometry (LC-DIA-MS) and using liquid-chromatography ion-mobility data independent acquisition mass spectrometry (LC-IM-DIA-MS). The inclusion of TWIMS was assessed for the effect on sample throughput, data integrity, confidence of protein and peptide identification, and dynamic range. The number of identified proteins is significantly increased by an average of 84% while both the precursor and product mass accuracies are maintained between the modalities. Sample dynamic range is also maintained while quantitation is achieved for all but the most abundant proteins by incorporating a novel data interpretation method that allows accurate quantitation to occur. This additional separation is all achieved within a workflow with no discernible deleterious effect on throughput. Consequently, TWIMS greatly enhances proteome coverage and can be reliably used for quantification when using an alternative product ion quantification strategy. Using TWIMS in biomarker discovery in human plasma is thus recommended. PMID:24397486

  19. Qualitative and quantitative characterization of plasma proteins when incorporating traveling wave ion mobility into a liquid chromatography-mass spectrometry workflow for biomarker discovery: use of product ion quantitation as an alternative data analysis tool for label free quantitation.

    PubMed

    Daly, Charlotte E; Ng, Leong L; Hakimi, Amirmansoor; Willingale, Richard; Jones, Donald J L

    2014-02-18

    Discovery of protein biomarkers in clinical samples necessitates significant prefractionation prior to liquid chromatography-mass spectrometry (LC-MS) analysis. Integrating traveling wave ion mobility spectrometry (TWIMS) enables in-line gas phase separation which when coupled with nanoflow liquid chromatography and data independent acquisition tandem mass spectrometry, confers significant advantages to the discovery of protein biomarkers by improving separation and inherent sensitivity. Incorporation of TWIMS leads to a packet of concentrated ions which ultimately provides a significant improvement in sensitivity. As a consequence of ion packeting, when present at high concentrations, accurate quantitation of proteins can be affected due to detector saturation effects. Human plasma was analyzed in triplicate using liquid-chromatography data independent acquisition mass spectrometry (LC-DIA-MS) and using liquid-chromatography ion-mobility data independent acquisition mass spectrometry (LC-IM-DIA-MS). The inclusion of TWIMS was assessed for the effect on sample throughput, data integrity, confidence of protein and peptide identification, and dynamic range. The number of identified proteins is significantly increased by an average of 84% while both the precursor and product mass accuracies are maintained between the modalities. Sample dynamic range is also maintained while quantitation is achieved for all but the most abundant proteins by incorporating a novel data interpretation method that allows accurate quantitation to occur. This additional separation is all achieved within a workflow with no discernible deleterious effect on throughput. Consequently, TWIMS greatly enhances proteome coverage and can be reliably used for quantification when using an alternative product ion quantification strategy. Using TWIMS in biomarker discovery in human plasma is thus recommended. PMID:24397486

  20. Fractionation of vanadium complexes in serum, packed cells and tissues of Wistar rats by means of gel filtration and anion-exchange chromatography

    Microsoft Academic Search

    Koen De Cremer; Marijn Van Hulle; Cyrille Chéry; Rita Cornelis; Karel Strijckmans; Richard Dams; Norbert Lameire; Raymond Vanholder

    2002-01-01

    Male Wistar rats were intraperitoneally injected with [ 48V]vanadium tracer to (1) investigate the distribution of vanadium over different tissues and (2) study the distribution of vanadium over the proteins and peptides in serum, packed cells and homogenates of tissues by means of liquid chromatography experiments (size exclusion, ion exchange). Target organs were primarily kidney, bone, spleen and liver. In

  1. Identification of chlorinated fatty acids in fish by gas chromatography/mass spectrometry with negative ion chemical ionization of pentafluorobenzyl esters.

    PubMed

    Zhuang, Wenshan; McKague, A Bruce; Reeve, Douglas W; Carey, John H

    2004-01-01

    This paper reports the development of a technique for identifying and confirming chlorinated fatty acids previously detected in fish by gas chromatography (GC) with halogen-specific detection (XSD). Fatty acid methyl esters (FAMEs) including chlorinated FAMEs within fractions of reversed-phase high-performance liquid chromatography of transesterified fish extracts were derivatized to pentafluorobenzyl esters, which were subjected to GC/mass spectrometry (MS) with negative ion chemical ionization (NICI). Pentafluorobenzyl esters displayed reasonably good GC characteristics, a very high ionization efficiency and a low degree of fragmentation. Chloride ion chromatograms extracted at m/z 35 and 37 from full scans were utilized for locating traces of chlorinated unknowns in the GC elution profile so that their mass spectra could be readily displayed. Significant ions displayed in the mass spectrum scanned in a narrow range of retention time where a chlorinated unknown was located were evaluated using ion chromatograms extracted at the m/z of these ions. The chromatographic peaks of those ions derived from the analyte were expected to center at that specific retention time, whereas those originating from matrix compounds were not. The isotopic patterns of chlorinated ions were also examined against their theoretical relative abundances. Using this approach, three metabolism-related dichloro fatty acids previously identified by GC/XSD in filet extracts of white sucker sampled downstream from a bleached kraft pulp mill were confirmed: dichlorooctadecanoic, dichlorohexadecanoic and dichlorotetradecanoic acids. In addition, an isomer of dichlorotetradecanoic acid was found in a reference fish sample. As sample preparation is critical in this application, improved conditions for hydrolysis and pentafluorobenzyl esterification are also discussed. PMID:14760613

  2. Chemometric Analysis of Gas Chromatography – Mass Spectrometry Data using Fast Retention Time Alignment via a Total Ion Current Shift Function

    SciTech Connect

    Nadeau, Jeremy S.; Wright, Bob W.; Synovec, Robert E.

    2010-04-15

    A critical comparison of methods for correcting severely retention time shifted gas chromatography-mass spectrometry (GC-MS) data is presented. The method reported herein is an adaptation to the Piecewise Alignment Algorithm to quickly align severely shifted one-dimensional (1D) total ion current (TIC) data, then applying these shifts to broadly align all mass channels throughout the separation, referred to as a TIC shift function (SF). The maximum shift varied from (-) 5 s in the beginning of the chromatographic separation to (+) 20 s toward the end of the separation, equivalent to a maximum shift of over 5 peak widths. Implementing the TIC shift function (TIC SF) prior to Fisher Ratio (F-Ratio) feature selection and then principal component analysis (PCA) was found to be a viable approach to classify complex chromatograms, that in this study were obtained from GC-MS separations of three gasoline samples serving as complex test mixtures, referred to as types C, M and S. The reported alignment algorithm via the TIC SF approach corrects for large dynamic shifting in the data as well as subtle peak-to-peak shifts. The benefits of the overall TIC SF alignment and feature selection approach were quantified using the degree-of-class separation (DCS) metric of the PCA scores plots using the type C and M samples, since they were the most similar, and thus the most challenging samples to properly classify. The DCS values showed an increase from an initial value of essentially zero for the unaligned GC-TIC data to a value of 7.9 following alignment; however, the DCS was unchanged by feature selection using F-Ratios for the GC-TIC data. The full mass spectral data provided an increase to a final DCS of 13.7 after alignment and two-dimensional (2D) F-Ratio feature selection.

  3. [High speed separation and quantitation of Ralstonia solanacearum of different virulence using high performance ion exchange chromatography].

    PubMed

    Lin, Juan; Ma, Cheng; Liu, Shutao; Wu, Lingling; Rao, Pingfan

    2007-01-01

    High performance ion exchange chromatography coupled with laser light scattering instrument was employed for the rapid separation and quantitation of Ralstonia solanacearum of different virulence. The pure culture of Ralstonia solanacearum was successfully separated into three characteristic fractions. Each fraction was collected and inoculated onto 2,3,5-triphenyltetrazolium chloride (TTC) plates to identify its virulence. The shapes and colors of the colonies were imaged, and the average attenuation index (attenuation index = red spot diameter of colony/total colony diameter) of ten colonies of each fraction was carefully determined. Furthermore, each fraction was inoculated into SPA liquid media at 30 degrees C with shaking (200 r/min) for 48 h, the cells were harvested, suspended at a density of 1.2 x 10(9) cfu/mL, and applied to infect tomato tissue culture plantlets using leaf-cutting method. The infection mortality of the tomato tissue culture plantlets was recorded from 1 to 9 days after inoculation. The results showed that the virulences of each fraction were different on the basis of attenuation index and infection mortality. The virulence of peak 3 fraction was the strongest. On the contrary, the virulence of peak 1 fraction was the weakest. In addition, the linear relationships between different injection volumes (1 - 180 microL) and their peak areas were investigated. The linearity was good within the range of the bacterial number of 9 x 10(6) - 9 x 10(8) (r = 0.99). This method can be potentially used as a novel tool for the rapid separation and quantitation of Ralstonia solanacearum of different virulences. PMID:17432579

  4. Determination of O-isopropyl methylphosphonic acid in living microorganism-agar matrixes using ion chromatography conductivity detection.

    SciTech Connect

    Nassar, Alaa F. (BCO); Lucas, Samuel V. (BCO); Thomas, Susan A. (BATTELLE (PACIFIC NW LAB))

    1999-01-01

    A direct an anion exchange, ion chromatography (IC)-based method for the detection of the chemical warfare agent surrogate O-isopropyl methylphosphonic acid (IMPA) in agar medium has been developed. This is the first report of the systematic development and validation of an IC-based method for the analysis of the chemical warfare agent degradation product, IMPA, in Petri dishes containing the agar medium with 10, 100 and 1000 mg/mL IMPA. Samples were prepared by dilution of the agar medium with deionized water followed by sonication and then filtration before the analysis by IC/conductivity detection. Using this method, the amount of IMPA in the Petri dishes was measured. Excellent separation efficiency and freedom from interference due to common anions such as phosphate and sulfate was obtained in the developed methods. Retention time precision is less than 1.0% relative standard deviation (%RSD) and the detection limit is 0.1 mg/mL. Three calibration curves were performed over the range 1-100 mg/mL using blank agar matrices spiked with five IMPA concentrations; with correlation coefficients (R{sup 2}) of 0.993, 0.991, and 0.992 for the calibration standard without dilution of agar matrix, at 4-times dilution and at 40-times dilution, respectively. Using three different samples at three IMPA spike levels, analysis accuracy was assessed by spiking the actual agar samples with IMPA. Average recoveries were 76, 79, and 84% for 10, 100, and 1000 mg/mL, respectively.

  5. Determination of propionylpromazine hydrochloride in formulation matrixes using reversed-phase ion-pair small bore liquid chromatography.

    PubMed

    Hurlbut, D B; Primus, T M; Goodall, M J; Volz, S A; Johnston, J J

    1999-01-01

    Propionylpromazine hydrochloride (PPZHCl) has been investigated for use with leghold traps to reduce the amount of self-inflicted trauma experienced by animals restrained by these traps. Three types of PPZHCl formulations made with Karo dark syrup, K-Y Jelly, and Vaseline were used in 2 types of tranquilizer trap devices (TTDs). A reversed-phase ion-pair liquid chromatography (LC) method using a small bore C18 column was used to: (1) determine the purity of the PPZHCl material used in these formulations, and (2) to determine the resulting PPZHCl content of each formulation. Analyte quantitation was done using UV absorption at 280 nm. Regression analysis of calibration standard solutions indicated a linear and directly proportional relationship between analyte response and PPZHCl concentration over the range evaluated. Recovery data from: (1) Vaseline formulations containing 38.8, 16.2, and 8.78% PPZHCl were 104, 92.9, and 90.2%, respectively, (2) Karo dark syrup formulations containing 26.5, 18.1, and 10.3% PPZHCl were 97.7, 99.3, and 106%, respectively, and (3) K-Y Jelly formulations containing 33.0, 23.5, and 13.4% PPZHCl were 100, 99.4, and 88.7%, respectively. The relative standard deviation (RSD) values from triplicate analysis of these formulations ranged from 0.7 to 6.7%. The PPZHCl content from 9 manufactured TTDs, 3 for each formulation type, were analyzed in triplicate and produced RSD values ranging from 0.7-6.8%. These results indicate that the formulation extraction presented could be used to evaluate the PPZHCl content in TTDs prior to field use. The use of a small bore LC column reduced the amount of solvents consumed and hazardous waste generated, compared to sample analysis that uses a more conventional analytical LC column. PMID:10589483

  6. Simultaneous determination of total nitrogen and total phosphorus in environmental waters using alkaline persulfate digestion and ion chromatography.

    PubMed

    De Borba, Brian M; Jack, Richard F; Rohrer, Jeffrey S; Wirt, Joan; Wang, Dongmei

    2014-11-21

    An ion chromatography (IC) method was developed for the simultaneous determination of total nitrogen and total phosphorus after alkaline persulfate digestion. This study takes advantage of advances in construction of high-resolution, high-capacity anion-exchange columns that can better tolerate the matrices typically encountered when a determination of total nitrogen and total phosphorous is required. Here, we used an electrolytically generated hydroxide eluent combined with a high-capacity, hydroxide-selective, anion-exchange column for the determination of total nitrogen (as nitrate-N) and total phosphorus (as phosphate-P) in environmental samples by IC. This method yielded LODs for nitrate-N and phosphate-P of 1.0 and 1.3 ?g/L, respectively. The LOQs determined for these analytes were 3.4 and 4.2 ?g/L, respectively. Due to the dilution factor required and the blank nitrate-N concentration after the persulfate digestion, the quantification limits increased for nitrate-N and phosphate-P to 171 and 63 ?g/L, respectively. The suitability of the method was evaluated by determining the nitrogen and phosphorus concentrations from known concentrations of organic-containing nitrogen and phosphorus compounds. In addition, environmental samples consisting of six different wastewaters and 48 reservoir samples were evaluated for total nitrogen and phosphorus. The recoveries of nitrogen and phosphorus from the organic-containing compounds ranged from 93.1 to 100.1% and 85.2 to 97.1%, respectively. In addition, good correlation between results obtained by the colorimetric method and IC was also observed. The linearity, accuracy, and evaluation of potential interferences for determining TN and TP will be discussed. PMID:25441080

  7. Simultaneous determination of aliskiren and hydrochlorothiazide in tablets and spiked human urine by ion-pair liquid chromatography.

    PubMed

    Belal, F; Walash, M; El-Enany, N; Zayed, S

    2013-12-01

    An alternative method for analysis of aliskiren (ALI) and hydrochlorothiazde (HCT) in combined dosage forms by ion-pair reversed phase high performance liquid chromatography was developed and validated. The pharmaceutical preparations were analyzed using a C18 column (250 mm x 4.6 mm, 3 microm) with a mobile phase consisting of 25% methanol, 50% sodium monobasic phosphate aqueous solution containing 6 mM tetrabutylammonium bromide and 25% water at pH 7.2. Isocratic analysis was performed at a flow rate of 1 mL/min and a column temperature of 30 degrees C under direct UV detection at 210 nm. Paracetamol was used as internal standard. The validation was performed according to the ICH guidelines. The proposed method was linear over the concentration range of 0.250 to 60 and 0.1 to 10 microg/mL for ALI and HCT, respectively. The limits of detection and quantitation (LOD and LOQ) were 0.075 and 0.198 microg/mL, respectively, for ALI and 0.04 and 0.062 microg/mL, respectively, for HCT. The method proved to be specific, sensitive, precise and accurate with mean recovery values of 101.1 +/- 0.32% and 100.9 +/- 0.41% for ALI and HCT, respectively. The method robustness was evaluated by means of an experimental design. The proposed method was applied successfully to spiked human urine samples with mean recoveries of 98.8 +/- 0.36% and 98.1 +/- 0.21% for ALI and HCT, respectively. PMID:24400438

  8. Immobilized metal ion affinity chromatography on Co2+-carboxymethylaspartate-agarose Superflow, as demonstrated by one-step purification of lactate dehydrogenase from chicken breast muscle.

    PubMed

    Chaga, G; Hopp, J; Nelson, P

    1999-02-01

    A rapid method for the purification of lactate dehydrogenase from whole chicken muscle extract in one chromatographic step is reported. The purification procedure can be accomplished in less than 1 h. A new type of immobilized metal ion affinity chromatography adsorbent is used that can be utilized at linear flow rates higher than 5 cm/min. The final preparation of the enzyme was with purity higher than 95% as ascertained by SDS-PAGE. Three immobilized metal ions (Ni2+, Zn2+ and Co2+) were compared for their binding properties towards the purified enzyme. The binding site of the enzyme for immobilized intermediate metal ions was determined after cleavage with CNBr and binding studies of the derivative peptides on immobilized Co2+. A peptide located on the N-terminus of the enzyme, implicated in the binding, has great potential as a purification tag in fusion proteins. PMID:9889081

  9. Determination of microbial fatty acid profiles at femtomolar levels in human urine and the initial marine microfouling community by capillary gas chromatography-chemical ionization mass spectrometry with negative ion detection

    Microsoft Academic Search

    Goran Odham; Anders Tunlid; Gunilla Westerdahl; Lennart Larsson; James B. Guckert; David C. White

    1985-01-01

    Summary Room temperature esterification with the electron capturing pentafluorobenzyl bromide in glass capillaries, with analysis by capillary gas-liquid chromatography coupled with chemical ionization mass spectrometry and negative ion detection in the selected ion mode, allowed detection and identification of fatty acids from micro- bial biofilms at the femtomolar level. This sensitivity was achieved without loss of specificity of the mass

  10. Biomonitoring of Aristolactam-DNA Adducts in Human Tissues using Ultra-Performance Liquid Chromatography/Ion-Trap Mass Spectrometry

    PubMed Central

    Yun, Byeong Hwa; Rosenquist, Thomas; Sidorenko, Viktoriya; Iden, Charles; Chung-Hsin, Chen; Pu, Yeong-Shiau; Bonala, Radha; Johnson, Francis; Dickman, Kathleen G.; Grollman, Arthur P.; Turesky, Robert J.

    2012-01-01

    Aristolochic acids (AAs) are a structurally-related family of nephrotoxic and carcinogenic nitrophenanthrene compounds found in Aristolochia herbaceous plants, many of which have been used worldwide for medicinal purposes. AAs have been implicated in the etiology of so-called Chinese herbs nephropathy and of Balkan endemic nephropathy. Both of these disease syndromes are associated with carcinomas of the upper urinary tract (UUC). 8-Methoxy-6-nitrophenanthro-[3,4-d]-1,3-dioxolo-5-carboxylic acid (AA-I) is a principal component of Aristolochia herbs. Following metabolic activation, AA-I reacts with DNA to form aristolactam (AL-I)-DNA adducts. We have developed a sensitive analytical method, using ultra-performance liquid chromatography-electrospray ionization/multistage mass spectrometry (UPLC-ESI/MSn) with a linear quadrupole ion-trap mass spectrometer, to measure 7-(deoxyadenosin-N6-yl) aristolactam I (dA-AL-I) and 7-(deoxyguanosin-N2-yl) aristolactam I (dG-AL-I) adducts. Using 10 ?g of DNA for measurements, the lower limits of quantitation of dA-AL-I and dG-AL-I are, respectively, 0.3 and 1.0 adducts per 108 DNA bases. We have used UPLC-ESI/MSn to quantify AL-DNA adducts in tissues of rodents exposed to AA, and in the renal cortex of patients with UUC who reside in Taiwan, where the incidence of this uncommon cancer is the highest reported for any country in the world. In human tissues, dA-AL-I was detected at levels ranging from 9 to 338 adducts per 108 DNA bases, whereas dG-AL-I was not found. We conclude that UPLC-ESI/MSn is a highly sensitive, specific and robust analytical method, positioned to supplant 32P-postlabeling techniques currently used for biomonitoring of DNA adducts in human tissues. Importantly, UPLC-ESI/MSn could be used to document exposure to AA, the toxicant responsible for AA nephropathy and its associated UUC. PMID:22515372

  11. Field detection and identification of a bioaerosol suite by pyrolysis-gas chromatography-ion mobility spectrometry

    NASA Astrophysics Data System (ADS)

    Snyder, A. Peter; Tripathi, Ashish; Maswadeh, Waleed M.; Ho, Jim; Spence, Mel

    2002-06-01

    Improvements were made to a pyrolysis-gas chromatography-ion mobility spectrometry stand-alone biodetector to provide more pyrolyzate compound information to the IMS detector module. Air carrier gas flowing continuously through the pyrolysis tube, the rate of air flow, and pyrolysis rate were found to improve the relative quality and quantity of pyrolyzate compounds detected by the IMS detector compare to earlier work. These improvements allowed a greater degree of confidence in the correlation of biological aerosols obtain in outdoor testing scenarios to a standard GC-IMS biological aerosol dataset. The airflow improvement allowed more biomarker compounds to be observed in the GC-IMS data domain for aerosols of Gram-negative Erwinia herbicola (EH) and ovalbumin protein as compared to previous studies. Minimal differences were observed for Gram-positive spores of Bacillus subtilis var. globigii (BG) from that of earlier work. Prior outdoor aerosol challenges dealt with the detection of one organism, either EH or BG. Biological aerosols were disseminated in a Western Canadian prairie and the Py-GC-IMS was tested for its ability to detect the biological aerosols. The current series of outdoor trials consisted of three different biological aerosol challenges. Forty-two trials were conducted and a simple area calculation of the GC-IMS data domain biomarker peaks correlated with the correct bioaerosol challenge in 30 trials. In another 7 trials, the status of an aerosol was determined to be biological in origin. Two additional trials had no discernible, unambiguous GC-IMS biological response, because they were black water sprays. Reproducible limits of detection were at a concentration of less than 0.5 bacterial analyte-containing particles per liter of air (ACPLA). In order to realize this low concentration, an aerosol concentrator was used to concentrate 2000 liters of air in 2.2 minutes. Previous outdoor aerosol trials have shown the Py-GC-IMS device to be a credible detector with response to determining the presence of a biological aerosol. The current series of outdoor trials has provided a platform to show that the Py-PC-IMS can provide information more specific than a biological or non-biological analysis to an aerosol when the time of dissemination is unknown to the operator. The Py-GC-IMS is shown to be able to discriminate between aerosols of a Gram-positive spore, a Gram-negative bacterium and a protein.

  12. Analysis of polychlorinated dibenzo- p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls in vegetable oil samples by gas chromatography–ion trap tandem mass spectrometry

    Microsoft Academic Search

    J. Malavia; M. Abalos; F. J. Santos; E. Abad; J. Rivera; M. T. Galceran

    2007-01-01

    Gas chromatography coupled to ion trap tandem mass spectrometry (CG–MS–MS) has been evaluated for the analysis of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in vegetable oil samples containing different concentration levels (0.2–6pgWHO-TEQg?1 for both PCDD\\/Fs and dl-PCBs) of the 29 toxic congeners of PCDD\\/F and dioxin-like PCBs. The effect of potential interfering compounds such as

  13. Analysis of cocaine and its principal metabolites in waste and surface water using solid-phase extraction and liquid chromatography–ion trap tandem mass spectrometry

    Microsoft Academic Search

    Adriana Gheorghe; Alexander van Nuijs; Bert Pecceu; Lieven Bervoets; Philippe G. Jorens; Ronny Blust; Hugo Neels; Adrian Covaci

    2008-01-01

    A validated method based on solid-phase extraction (SPE) and liquid chromatography–ion trap tandem mass spectrometry (LC-MS\\/MS)\\u000a is described for the determination of cocaine (COC) and its principal metabolites, benzoylecgonine (BE) and ecgonine methyl\\u000a ester (EME), in waste and surface water. Several SPE adsorbents were investigated and the highest recoveries (95.7?±?5.5,\\u000a 91.8?±?2.2 and 72.5?±?5.3% for COC, BE and EME, respectively) were

  14. Use of 1-(2-pyridylazo)-2-naphthol as the post column reagent for ion exchange chromatography of heavy metals in environmental samples

    Microsoft Academic Search

    Supalax Srijaranai; Wijitra Autsawaputtanakul; Yanawath Santaladchaiyakit; Tipwan Khameng; Archava Siriraks; Richard L. Deming

    2011-01-01

    Ion exchange chromatography (IEC) using a bi-functional column (quaternary ammonium and sulfonate groups), followed by post-column reaction (PCR) with 1-(2-pyridylazo)-2-naphthol (PAN), was used to separate and quantitate Cu(II), Ni(II), Zn(II), Co(II), Cd(II), Mn(II) and Hg(II) at low concentration levels. IEC–PCR separation was achieved within 14min using the mobile phase containing 3mmolL?1 2,6-pyridinedicarboxylic acid (PDCA) and 3mmolL?1 oxalate at pH 12.5.

  15. Separation of N-nitrosoamino acids by C 18 reversed-phase ion-pair high-performance liquid chromatography and compatible detection by electrospray ionization mass spectrometry

    Microsoft Academic Search

    C. F. Cheng; C. W. Tsang

    1999-01-01

    Four non-volatile N-nitrosoamino acids, namely N-nitrososarcosine, N-nitrosoproline, N-nitrosothiazolidine-4-carboxylic acid and N-nitroso-2-methyl-thiazolidine-4-carboxylic acid were separated by C18 reversed-phase ion-pair high-performance liquid chromatography (HPLC) using 1.4 mM C16-cetyltrimethylammonium chloride in methanol–water–acetonitrile (60:35:5, v\\/v) as the mobile phase. The N-nitrosoamino acids were sensitively detected by negative electrospray ionization mass spectrometry (ESI-MS) in the form of the deprotonated carboxylate anion, [M?H]?. Compatibility problems associated

  16. Determination of trace labile copper in environmental waters by magnetic nanoparticle solid phase extraction and high-performance chelation ion chromatography.

    PubMed

    Wei, Z; Sandron, S; Townsend, A T; Nesterenko, P N; Paull, B

    2015-04-01

    Cobalt magnetic nanoparticles surface functionalised with iminodiacetic acid were evaluated as a nano-particulate solid phase extraction absorbent for copper ions (Cu(2+)) from environmental water samples. Using an external magnetic field, the collector nanoparticles could be separated from the aqueous phase, and adsorbed ions simply decomplexed using dilute HNO3. Effects of pH, buffer concentration, sample and sorbent volume, extraction equilibrium time, and interfering ion concentration on extraction efficiency were investigated. Optimal conditions were then applied to the extraction of Cu(2+) ions from natural water samples, prior to their quantitation using high-performance chelation ion chromatography. The limits of detection (LOD) of the combined extraction and chromatographic method were ~0.1 ng ml(-1), based upon a 100-fold preconcentration factor (chromatographic performance; LOD=9.2 ng ml(-1) Cu(2+)), analytical linear range from 20 to 5000 ng mL(-1), and relative standard deviations=4.9% (c=1000 ng ml(-1), n=7). Accuracy and precision of the combined approach was verified using a certified reference standard estuarine water sample (SLEW-2) and comparison of sample determinations with sector field inductively coupled plasma mass spectrometry. Recoveries from the addition of Cu(2+) to impacted estuarine and rain water samples were 103.5% and 108.5%, respectively. Coastal seawater samples, both with and without prior UV irradiation and dissolved organic matter removal were also investigated using the new methodology. The effect of DOM concentration on copper availability was demonstrated. PMID:25640140

  17. Steroids in porcine follicular fluid: analysis by HPLC, capillary CG and capillary CG/MS after purification on SEP-PAK C18 and ion exchange chromatography.

    PubMed

    Khalil, M W; Lawson, V

    1983-04-01

    Steroids in porcine follicular fluid have been concentrated by reverse phase chromatography in SEP-PAK C18 and purified further on the cation exchanger SP-Sephadex C-25. Fractionation into unconjugated neutral and phenolic steroids, glucuronides and sulfates was carried out on triethylaminohydroxypropyl Sephadex LH-20 (TEAP-LH-20). The unconjugated neutral fraction was analysed by high pressure liquid chromatography (HPLC) on a C18 radial cartridge 5 mm I.D.; 10 mu, or on a C18 5 mu RESOLVE column, and by capillary gas chromatography (GC) on a 12 M OV-1 cross linked fused silica column. Testosterone, progesterone and androstenedione were the major steroids detected by HPLC monitored at 254 nm, although 17- hydroxy-, 20 alpha-dihydro- and 20 beta-dihydroprogesterone were also present. Pregnenolone, pregnanediol, dehydroepiandrosterone, 17-hydroxypregnenolone and androsterone were detected by capillary CG as their 0-methyloxime trimethylsilyether derivatives. Further confirmation of structure was provided by complete mass spectral data or by selective ion monitoring (SIM). PMID:6658891

  18. Applying Chromatography.

    ERIC Educational Resources Information Center

    Klein, Jessie W.; Patev, Paul

    1998-01-01

    Presents three experiments to introduce students to different kinds of chromatography: (1) paper chromatography; (2) gel filtration chromatography; and (3) reverse-phase liquid chromatography. Written in the form of a laboratory manual, explanations of each of the techniques, materials needed, procedures, and a glossary are included. (PVD)

  19. Studies on the analysis of food additives by high-performance liquid chromatography. V. Simultaneous determination of preservatives and saccharin in foods by ion-pair chromatography.

    PubMed

    Terada, H; Sakabe, Y

    1985-10-18

    A high-performance liquid chromatographic method for the simultaneous determination of sorbic acid, benzoic acid, p-hydroxybenzoic acid and its methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl esters and saccharin in foodstuffs is described. For good separations of these compounds, acetonitrile-water-0.2 M phosphate buffer pH 3.6 (7:12:1) containing 2 mM cetyltrimethylammonium bromide as an ion-pair reagent and a Nucleosil 5C18 column are required. A steam distillation method and a Sep-Pak C18 cartridge method for the sample preparation are compared. The recoveries from a coffee drink were generally better than 93.8% and the relative standard deviations were 0.85-2.15% for the Sep-Pak C18 cartridge method. PMID:4086620

  20. Evaluation of a monolithic silica column operated in the hydrophilic interaction chromatography mode with evaporative light scattering detection for the separation and detection of counter-ions.

    PubMed

    Pack, Brian W; Risley, Donald S

    2005-05-01

    In this work a monolithic silica column operated in the hydrophilic interaction chromatography (HILIC) mode in conjunction with an evaporative light scattering detector (ELSD) was investigated. Lithium, sodium and potassium were used as the test counter-ions for this evaluation. Chromatographic properties of this column operated in the HILIC mode were determined by varying key mobile phase parameters, such as pH, flow rate, buffer strength, acid and organic modifier. As organic content was increased from 60 to 90% acetonitrile, retention time increased on average by a factor of seven for the test cations listed above. Buffer concentration and pH were also observed to have an effect, although not as significant as the HILIC effect that was observed by changing organic content. Flow rates up to 5 mL/min were utilized to perform counter-ion separations in less than 3 min. After examining the changes in retention, resolution, and peak shape an optimized method was established and then further evaluated for linearity, reproducibility, and limit of detection (LOD) for sodium. Linearity was acceptable with an R2 value of 0.999 across the working-standard range and a LOD of 0.1 microg/mL was calculated. The reproducibility on the counter-ion determination from pharmaceutical sodium salts was 1.6% R.S.D. on average, and the accuracy of the counter-ion prediction was approximately 3% from theory when salt content was corrected for potency. PMID:15909529

  1. Effect of humic acid on absorption-release processes in the bottom sediments-Yenisei river water system as studied by dual-column ion chromatography and ?-ray spectrometry

    Microsoft Academic Search

    L. G. Bondareva; O. P. Kalyakina; A. Ya. Bolsunovskii

    2006-01-01

    The effect of humic acid on absorption-release processes in the bottom sediments-Yenisei river water system was studied by\\u000a dual-column ion chromatography and ?-ray spectrometry. With the use of ion chromatography, it was found that processes related\\u000a to the absorption of SO\\u000a 4\\u000a 2?\\u000a and Cl? anions by a solid phase with the release of NO\\u000a 3\\u000a ?\\u000a , PO\\u000a 4

  2. Size-exclusion chromatography with on-line ultraviolet, proton nuclear magnetic resonance and mass spectrometric detection and on-line collection for off-line Fourier transform infrared spectroscopy.

    PubMed

    Ludlow, M; Louden, D; Handley, A; Taylor, S; Wright, B; Wilson, I D

    1999-10-01

    The coupling of HPLC with UV detection and on-line NMR spectroscopy and mass spectrometry combined with a dedicated interface for the collection of the chromatographic eluent for subsequent Fourier transform (FT) IR has been investigated using a number of polymer additives as model compounds. Size-exclusion chromatography was performed using deuterated chloroform as eluent with the separation monitored on-line by UV detection at 254 nm and on-flow 1H-NMR and MS. The effluent from the NMR probe was directed to a dedicated HPLC interface where it was deposited on a germanium plate for subsequent FT-IR. NMR and MS spectra were successfully obtained for 2,6-di-tert.-butyl-4-methylphenol, octadecyl-3-(3,5-di-tert.-butyl-4-hydroxyphenyl) propionate (Irganox 1076) and diisooctyl phthalate on-line and FT-IR spectra for all three compounds were obtained off-line. Practical problems encountered with this multiple hyphenation are described. PMID:10536827

  3. High-performance liquid chromatography with paired ion electrospray ionization (PIESI) tandem mass spectrometry for the highly sensitive determination of acidic pesticides in water.

    PubMed

    Xu, Chengdong; Armstrong, Daniel W

    2013-08-20

    A novel method based on the paired ion electrospray ionization (PIESI) mass spectrometry has been developed for determination of acidic pesticides at ultratrace levels in surface and ground waters. The proposed approach provides greatly enhanced sensitivity for acidic pesticides and overcomes the drawbacks of the less sensitive negative ion mode ESI-MS. The limits of detection (LODs) of 19 acidic pesticides were evaluated with four types of dicationic ion-pairing reagent (IPR) in both single ion monitoring (SIM) and selected reaction monitoring (SRM) mode. The LOD of 19 pesticides obtained with the use the optimal dicationic ion-pairing reagent ranged from 0.6pg to 19pg, indicating the superior sensitivity provided by this method. The transition pathways for different pesticide-IPR complexes during the collision induced dissociation (CID) were identified. To evaluate and eliminate any matrix effects and further decrease the detection limits, off-line solid-phase extraction (SPE) was performed for DI water and a river water matrix spiked with 2000ng L(-1) and 20ng L(-1) pesticides standards respectively, which showed an average percent recovery of 93%. The chromatographic separation of the acidic pesticides was conducted by high-performance liquid chromatography (HPLC) using a C18 column (250mm×2.1mm) in the reversed phase mode using linear gradient elution. The optimized HPLC-PIESI-MS/MS method was utilized for determination of acidic pesticide at ng L(-1) level in stream/pond water samples. This experimental approach is 1-3 orders of magnitude more sensitive for these analytes than other reported methods performed in the negative ion mode. PMID:23910961

  4. Simultaneous qualitative and quantitative determination of phenolic compounds in Aloe barbadensis Mill by liquid chromatography-mass spectrometry-ion trap-time-of-flight and high performance liquid chromatography-diode array detector.

    PubMed

    Wu, Xiaofang; Ding, Wenjing; Zhong, Jiasheng; Wan, Jinzhi; Xie, Zhiyong

    2013-06-01

    An effective and comprehensive method was developed for the simultaneous analysis of phenolic compounds in the dried exudate of Aloe barbadensis Mill by liquid chromatography-mass spectrometry-ion trap-time-of-flight (LCMS-IT-TOF) and high performance liquid chromatography-diode array detector (HPLC-DAD). Qualitative analysis of all the compounds presented in A. barbadensis Mill was performed on LCMS-IT-TOF, and the diagnostic fragmentation patterns of different types of phenolic compounds (chromones, phenyl pyrones, naphthalene derivative, anthrones and anthraquinones) were discussed on the basis of ESI-IT-TOF MS of components in A. barbadensis Mill and eleven authentic standards. Under the optimal HPLC-DAD chromatographic conditions, quantification of 11 typical phenolic compounds in 15 batches of A. barbadensis Mill was achieved on an Agilent TC-C18 column using gradient elution with a solvent system of methanol and water at a flow rate of 1.0mLmin(-1) and detected at 230nm. All calibration curves exhibited good linear relationship (r(2)>0.9991). The relative standard deviation values for intraday precision were less than 2% with accuracies between 98.21% and 104.57%. The recoveries of the eleven analytes ranged from 97.53 to 105.00% with RSDs less than 2%. This is the first simultaneous characterization and quantitative determination of multiple phenolic compounds in A. barbadensis Mill from locally grown cultivars in China by LCMS-IT-TOF and HPLC-DAD, which can be applied to standardize the quality of A. barbadensis Mill and the future design of nutraceutical and cosmetic preparations. PMID:23542732

  5. Determination of diquat and paraquat in olive oil by ion-pair liquid chromatography–electrospray ionization mass spectrometry (MRM)

    Microsoft Academic Search

    María A. Aramendía; V. Borau; Fernando Lafont; Alberto Marinas; José M. Marinas; José M. Moreno; Juan M. Porras; Francisco J. Urbano

    2006-01-01

    For the first time a method for determination of herbicides diquat (DQ) and paraquat (PQ) in olive oil was developed utilising liquid chromatography–electrospray ionization mass spectrometry (MRM). n-Hexane\\/10mM HFBA aqueous solution partitioning was used as the extraction method. Separation was carried out in an Xterra C8 column (100×21mm, 3?m), using the gradient mode. Solvent A was a HFBA aqueous solution

  6. Direct analysis of carbohydrates in animal plasma by ion chromatography coupled with mass spectrometry and pulsed amperometric detection for use as a non-invasive diagnostic tool.

    PubMed

    Kotnik, Darja; Smidovnik, Andrej; Jazbec-Križman, Petra; Križman, Mitja; Prošek, Mirko

    2011-12-01

    The present paper demonstrates that electrochemical detection (ECD) coupled to ion chromatography and electrospray ionization tandem mass spectrometry (IC-ECD-ESI/MS/MS) can be used to rapidly estimate some indications of the health status of organisms. The lactulose to mannitol ratio (L/M) is used as a non-invasive assay to investigate small intestinal absorption pathways and mucosal integrity. In the present study, an evaluation of the negative effects of nonsteroidal anti-inflammatory drug meloxicam perorally administrated to a group of dogs was carried out by determining the lactulose/mannitol index using the IC-ECD-ESI/MS/MS hyphenated technique. According to the results of the study, meloxicam altered gastrointestinal permeability. Coenzyme Q(10) (CoQ(10)) was tested to determine if it could prevent meloxicam induced gastrointestinal damage and it was found that CoQ(10) could be an effective preventive treatment. Furthermore, plasma glucose concentration level was determined to be an indirect indicator of the oxidative state in the blood. To find out the beneficial effects of a double antioxidant combination (?-lipoic acid (ALA) and CoQ(10)) on the total glucose level in chickens, ALA and CoQ(10) were provided as food additives in factory farm raised chicken. The results of the pilot study indicate that the glucose level in the plasma of chickens group fed with CoQ(10) and ALA was significantly decreased compared to the control group. Ion chromatography (IC) utilizing pulsed amperometric detection (PAD) was compared to ion chromatography coupled with tandem mass spectrometry (MS/MS) as an analytical tool for monitoring the carbohydrate level in biological fluids. In electrochemical detection, the newly developed two-pulse waveform successfully withstands matrix effects in biological samples. Continuous on-line desalting of the high salt concentrations used as the eluent for carbohydrate separation from the anion-exchange column allows coupling of IC and MS techniques. A make-up solution (0.5mM LiCl) was delivered prior to MS detection for efficient ionization of eluted carbohydrates. Method validation showed that both used techniques are practically comparable and some advantages of each are presented. PMID:22041089

  7. Organic solvent and temperature-enhanced ion chromatography-high resolution mass spectrometry for the determination of low molecular weight organic and inorganic anions.

    PubMed

    Gilchrist, Elizabeth S; Nesterenko, Pavel N; Smith, Norman W; Barron, Leon P

    2015-03-20

    There has recently been increased interest in coupling ion chromatography (IC) to high resolution mass spectrometry (HRMS) to enable highly sensitive and selective analysis. Herein, the first comprehensive study focusing on the direct coupling of suppressed IC to HRMS without the need for post-suppressor organic solvent modification is presented. Chromatographic selectivity and added HRMS sensitivity offered by organic solvent-modified IC eluents on a modern hyper-crosslinked polymeric anion-exchange resin (IonPac AS18) are shown using isocratic eluents containing 5-50 mM hydroxide with 0-80% methanol or acetonitrile for a range of low molecular weight anions (<165 Da). Comprehensive experiments on IC thermodynamics over a temperature range between 20-45 °C with the eluent containing up to 60% of acetonitrile or methanol revealed markedly different retention behaviour and selectivity for the selected analytes on the same polymer based ion-exchange resin. Optimised sensitivity with HRMS was achieved with as low as 30-40% organic eluent content. Analytical performance characteristics are presented and compared with other IC-MS based works. This study also presents the first application of IC-HRMS to forensic detection of trace low-order anionic explosive residues in latent human fingermarks. PMID:25732588

  8. Mass Spectrometry Parameters Optimization for the 46 Multiclass Pesticides Determination in Strawberries with Gas Chromatography Ion-Trap Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Fernandes, Virgínia C.; Vera, Jose L.; Domingues, Valentina F.; Silva, Luís M. S.; Mateus, Nuno; Delerue-Matos, Cristina

    2012-12-01

    Multiclass analysis method was optimized in order to analyze pesticides traces by gas chromatography with ion-trap and tandem mass spectrometry (GC-MS/MS). The influence of some analytical parameters on pesticide signal response was explored. Five ion trap mass spectrometry (IT-MS) operating parameters, including isolation time (IT), excitation voltage (EV), excitation time (ET), maximum excitation energy or " q" value (q), and isolation mass window (IMW) were numerically tested in order to maximize the instrument analytical signal response. For this, multiple linear regression was used in data analysis to evaluate the influence of the five parameters on the analytical response in the ion trap mass spectrometer and to predict its response. The assessment of the five parameters based on the regression equations substantially increased the sensitivity of IT-MS/MS in the MS/MS mode. The results obtained show that for most of the pesticides, these parameters have a strong influence on both signal response and detection limit. Using the optimized method, a multiclass pesticide analysis was performed for 46 pesticides in a strawberry matrix. Levels higher than the limit established for strawberries by the European Union were found in some samples.

  9. Rapid speciation and determination of vanadium compounds using ion-pair reversed-phase ultra-high-performance liquid chromatography inductively coupled plasma-sector field mass spectrometry.

    PubMed

    Kilibarda, Nikola; Afton, Scott E; Harrington, James M; Yan, Fei; Levine, Keith E

    2013-08-23

    Environmental vanadium contamination is a potential concern to public health, as evidenced by its place on the U.S. Environmental Protection Agency Drinking Water Contaminant Candidate List as a priority contaminant. Vanadium toxicity varies significantly between different oxidation states; therefore, it is crucial to be able to monitor the speciation of vanadium in environmental samples. In this study, a novel method is described that utilizes ion-pair reversed-phase ultra-high-performance liquid chromatography with inductively coupled plasma-sector field mass spectrometry (IP-RP-UHPLC-ICP-SFMS) to separate vanadyl and vanadate ions and resolve a major polyatomic spectral interference ((35)Cl(16)O(+)) in less than a minute. Detection limits were obtained in the low ngL(-1) (part per trillion) range with linear calibrations across several orders of magnitude (50ngL(-1)-100?gL(-1)). The mechanism of chromatographic retention was elucidated through investigation of the role of ethylenediaminetetraacetic acid, tetrabutylammonium ion and pH on elution. The optimized method was then applied to the speciation of vanadium in local lake water samples. PMID:23871564

  10. Detection and chemical profiling of Ling-Gui-Zhu-Gan decoction by ultra performance liquid chromatography-hybrid linear ion trap-Orbitrap mass spectrometry.

    PubMed

    Wang, Pei; Wang, Bo; Xu, Jingyao; Sun, Jianbo; Yan, Qin; Ji, Bin; Zhao, Yunli; Yu, Zhiguo

    2015-02-01

    Ling-Gui-Zhu-Gan decoction (LGZGD), a well-known traditional Chinese medicine (TCM) formula, has been extensively used for the treatment of cardiovascular disease in clinic. However, the chemical constituents in LGZGD had not been investigated so far. In this study, an ultra performance liquid chromatography-hybrid electrospray ionization linear ion trap-Orbitrap mass spectrometry (UPLC-LTQ-Oribitrap-MS/MS) method was established for rapid separation and structural identification of the constituents in LGZGD. Separation was performed on an ACQUITY(TM) UPLC BEH C18 column (50 × 2.1 mm, 1.7 ?m) by gradient elution mode, using acetonitrile-water containing 0.1% formic acid as mobile phase at the flow rate of 0.2 mL/min. Accurate mass measurement for molecular ions and characteristic fragment ions could represent identification criteria for these compounds. As a result, 95 compounds including triterpene acids, triterpene saponins, flavonoids, coumarins, coumestans, benzofurans, phenylpropanoids and sesquiterpenoid lactones were detected, and 90 of them were tentatively identified. All compounds were further assigned in the individual raw material. In conclusion, the UPLC-LTQ-Orbitrap-MS/MS is a highly efficient technique to separate and identify constituents in complex matrices of TCMs. These results obtained in this research will provide a basis for quality control and further in vivo study of LGZGD. PMID:24920655

  11. Analysis of novel hydroperoxides and other metabolites of oleic, linoleic, and linolenic acids by liquid chromatography-mass spectrometry with ion trap MSn.

    PubMed

    Oliw, E H; Su, C; Skogström, T; Benthin, G

    1998-09-01

    Linoleate is oxygenated by manganese-lipoxygenase (Mn-LO) to 11S-hydroperoxylinoleic acid and 13R-hydroperoxyoctadeca-9Z,11E-dienoic acid, whereas linoleate diol synthase (LDS) converts linoleate sequentially to 8R-hydroperoxylinoleate, through an 8-dioxygenase by insertion of molecular oxygen, and to 7S,8S-dihydroxylinoleate, through a hydroperoxide isomerase by intramolecular oxygen transfer. We have used liquid chromatography-mass spectrometry (LC-MS) with an ion trap mass spectrometer to study the MSn mass spectra of the main metabolites of oleic, linoleic, alpha-linolenic and gamma-linolenic acids, which are formed by Mn-LO and by LDS. The enzymes were purified from the culture broth (Mn-LO) and mycelium (LDS) of the fungus Gaeumannomyces graminis. MS3 analysis of hydroperoxides and MS2 analysis of dihydroxy- and monohydroxy metabolites yielded many fragments with information on the position of oxygenated carbons. Mn-LO oxygenated C-11 and C-13 of 18:2n-6, 18:3n-3, and 18:3n-6 in a ratio of approximately 1:1-3 at high substrate concentrations. 8-Hydroxy-9(10)epoxystearate was identified as a novel metabolite of LDS and oleic acid by LC-MS and by gas chromatography-MS. We conclude that LC-MS with MSn is a convenient tool for detection and identification of hydroperoxy fatty acids and other metabolites of these enzymes. PMID:9778131

  12. Engineering of a metal coordinating site into human glutathione transferase M1-1 based on immobilized metal ion affinity chromatography of homologous rat enzymes.

    PubMed

    Chaga, G; Widersten, M; Andersson, L; Porath, J; Danielson, U H; Mannervik, B

    1994-09-01

    Rat glutathione transferase (GST) 3-3 binds to Ni(II)-iminodiacetic acid (IDA)-agarose, whereas other GSTs that are abundant in rat liver do not bind to this immobilized metal ion affinity chromatography (IMAC) adsorbent. Rat GST 3-3 contains two superficially located amino acid residues, His84 and His85, that are suitably positioned for coordination to Ni(II)-IDA-agarose. This particular structural motif is lacking in GSTs that do not bind to the IMAC matrix. Creation of an equivalent His-His structure in the homologous human GST M1-1 by protein engineering afforded a mutant enzyme that displays affinity for Ni(II)-IDA-agarose, in contrast to the wild-type GST M1-1. The results identify a distinct site that is operational in IMAC and suggest an approach to the rational design of novel integral metal coordination sites in proteins. PMID:7831282

  13. Separation and quantitation of phenolic compounds in mainstream cigarette smoke by capillary gas chromatography with mass spectrometry in the selected-ion mode.

    PubMed

    Nanni, E J; Lovette, M E; Hicks, R D; Fowler, K W; Borgerding, M F

    1990-05-01

    Cigarette smoke condensate is a complex chemical matrix and determination of phenolic compounds in it frequently requires extensive and laborious sample preparation. By utilizing derivatization techniques and capillary column gas chromatography with mass spectrometry in the selected-ion mode, separation and quantitation of selected phenolic compounds found in mainstream cigarette smoke can be accomplished with minimal sample preparation. This method has been used to determine concentrations of phenol, o-cresol, m-cresol, p-cresol, catechol, resorcinol and hydroquinone in cigarette smoke condensate from a number of commercially available cigarettes and a new cigarette which heats, but does not burn, tobacco. Unlike tobacco-burning cigarettes, levels of the phenolic compounds in the new cigarette smoke are at or below the detection limits for most of the compounds. This result is attributed to the unique design of the new cigarette. PMID:2355067

  14. Rapid Characterization and Identification of Flavonoids in Radix Astragali by Ultra-High-Pressure Liquid Chromatography Coupled with Linear Ion Trap-Orbitrap Mass Spectrometry.

    PubMed

    Zhang, Jing; Xu, Xiao-Jie; Xu, Wen; Huang, Juan; Zhu, Da-Yuan; Qiu, Xiao-Hui

    2015-07-01

    A simple and effective method was established for separation and characterization of flavonoid constituents in Radix Astragali (RA) by combination of ultra-high-pressure liquid chromatography with LTQ-Orbitrap tandem mass spectrometry (u-HPLC-LTQ-Orbitrap-MS(n)). For three major structural types of flavonoids, the proposed fragmentation pathways and major diagnostic fragment ions of isoflavones, pterocarpans and isoflavans were investigated to trace isoflavonoid derivatives in crude plant extracts. Based on the systematic identification strategy, 48 constituents were rapidly detected and characterized or tentatively identified, many of which were first reported in RA. The u-PHLC-LTQ-Orbitrap MS(n) platform was proved as an effective tool for rapid qualitative analysis of secondary metabolite productions from natural resources. PMID:25501118

  15. Determination of 14 amines in air samples using midget impingers sampling followed by analysis with ion chromatography in tandem with mass spectrometry.

    PubMed

    Verriele, Marie; Plaisance, Hervé; Depelchin, Laurence; Benchabane, Samia; Locoge, Nadine; Meunier, Guillaume

    2012-02-01

    An Ion Chromatography-Mass Spectrometry (IC-MS) method was developed for the simultaneous quantification of 14 volatile amines in air. The method includes collection of compounds into two midget impingers in a row filled with 15 ml of ultrapure water. The analytical performances with mass spectrometry detection were compared to those obtained with classical conductivity detection. The use of mass spectrometry detection (in SIM mode) overcomes most of the coelutions encountered with conductivity detection. Although the linearity domain of calibrations is reduced for the MS detection as compared with the CD detection, the detection limits in MS detection are highly lowered allowing the quantification of amines at the levels of ?g m(-3) in air with a good accuracy for most compounds (RSD of less than 10%). This method was successfully applied to the analysis of amines released from polyurethane foams. Seven amines were identified and some in high concentrations, like dimethylaminoethanol, NIAX and TEDA. PMID:22274792

  16. Development and validation of automatic HS-SPME with a gas chromatography-ion trap/mass spectrometry method for analysis of volatiles in wines.

    PubMed

    Paula Barros, Elisabete; Moreira, Nathalie; Elias Pereira, Giuliano; Leite, Selma Gomes Ferreira; Moraes Rezende, Claudia; Guedes de Pinho, Paula

    2012-11-15

    An automated headspace solid-phase microextraction (HS-SPME) combined with gas chromatography-ion trap/mass spectrometry (GC-IT/MS) was developed in order to quantify a large number of volatile compounds in wines such as alcohols, ester, norisoprenoids and terpenes. The procedures were optimized for SPME fiber selection, pre-incubation temperature and time, extraction temperature and time, and salt addition. A central composite experimental design was used in the optimization of the extraction conditions. The volatile compounds showed optimal extraction using a DVB/CAR/PDMS fiber, incubation of 5 ml of wine with 2g NaCl at 45 °C during 5 min, and subsequent extraction of 30 min at the same temperature. The method allowed the identification of 64 volatile compounds. Afterwards, the method was validated successfully for the most significant compounds and was applied to study the volatile composition of different white wines. PMID:23158309

  17. Metabolic profile of 2-(2-hydroxypropanamido) benzoic acid in rats by ultra high performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Guan, Jiao; Zhang, Qili; Rong, Rong; Han, Fei; Zhu, Heyun; Zhao, Yunli; Song, Aihua; Yu, Zhiguo

    2015-07-01

    An ultra high performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry (UHPLC-FT-ICR-MS) method was developed to investigate the in vivo metabolism of 2-(2-hydroxypropanamido) benzoic acid (HPABA), a marine-derived anti-inflammatory drug, for the first time. Plasma, urine, feces and bile samples were collected from male and female rats after a single intragastric administration of HPABA at a dose of 100mg/kg. Besides the parent drug, a total of 13 metabolites (3 phase I and 10 phase II metabolites) were detected and tentatively identified through comparing their mass spectrometry profiles with those of HPABA. Results demonstrated that metabolic pathways of HPABA in rats included decarboxylation, hydroxylation, dehydrogenation, glucuronidation, glycine conjugation and N-acetyl conjugation. In summary, this work provided valuable information regarding the metabolism of HPABA in rats, which would contribute to better understanding of its safety and mechanism of action. PMID:25988429

  18. Low-level bromate analysis in drinking water by ion chromatography with optimized suppressed conductivity cell current followed by a post-column reaction and UV\\/Vis detection

    Microsoft Academic Search

    Marcellin Fotsing; Benoit Barbeau; Michele Prevost

    2011-01-01

    In the present work, a high capacity anion exchange column was used to efficiently and simultaneously separate traces of oxyhalide disinfection byproducts (DBP) anions and bromide by an ion chromatography system followed by a post-column reaction (PCR). The PCR generates in situ hydroiodic (HI) acid from the excess of potassium iodate that combines with bromate from the column effluent to

  19. Analysis of 19-nortestosterone residue in animal tissues by ion-trap gas chromatography-tandem mass spectrometry

    Microsoft Academic Search

    Jin-qing Jiang; Lei Zhang; Guang-ling Li; Hai-tang Zhang; Xue-feng Yang; Jun-wei Liu; Ren-feng Li; Zi-liang Wang; Jian-hua Wang

    2011-01-01

    A rapid sample treatment procedure for the gas chromatography-tandem mass spectrometry (GC-MS) determination of 19-nortestosterone\\u000a (19-NT) in animal tissues has been developed. In our optimized procedures, enzymatic hydrolysis with ?-glucuronidase from\\u000a Escherichia coli was performed in an acetate buffer (pH 5.2, 0.2 mol\\/L). Next, the homogenate was mixed with methanol and heated at 60 °C\\u000a for 15 min, then placed

  20. Evaluation of on-line high-performance size-exclusion chromatography, differential refractometry, and multi-angle laser light scattering analysis for the monitoring of the oligomeric state of human immunodeficiency virus vaccine protein antigen.

    PubMed

    Barackman, John; Prado, Isaias; Karunatilake, Chulani; Furuya, Kenji

    2004-07-16

    Chiron has developed a novel mutant form of the human immunodeficiency virus (HIV) envelop protein, o-gp140, that is currently entering Human Phase 1 clinical trials for testing as a prophylactic HIV vaccine. The o-gp140 protein is oligomeric and the quaternary structure is thought to play an important role in its activity as an antigen. As o-gpl40 proceeds through the clinical trial process and prior to marketing approval, analytical methods that are able to demonstrate manufacturing consistency with respect to degree of oligomerization will need to be developed and validated. On-line high-performance size-exclusion chromatography, differential refractometry, and multi-angle laser light scattering analysis (HPSEC-RI-MALLS), a method commonly used to obtain the molar mass of macromolecules based on the Rayleigh-Gans-Debye approximation, was evaluated for this purpose. The results obtained demonstrated intra- and inter-day precisions to be 0.9 and 3.6% R.S.D., respectively. Accuracy was found to be equal to, or better than, 11% when comparing the known molar masses of test proteins to that of the molar masses determined by the method. Additionally, the method compared favorably to orthogonal native polyacrylamide gel electrophoresis and ultracentrifugation analyses. R-factor analysis was used to demonstrate that HPSEC-RI-MALLS is capable of discriminating compositional differences between o-gpl40 test lots. Based on the data presented, HPSEC-RI-MALLS may be a suitable manufacturing control method. PMID:15317413

  1. A rapid and accurate method for the quantitative estimation of natural polysaccharides and their fractions using high performance size exclusion chromatography coupled with multi-angle laser light scattering and refractive index detector.

    PubMed

    Cheong, Kit-Leong; Wu, Ding-Tao; Zhao, Jing; Li, Shao-Ping

    2015-06-26

    In this study, a rapid and accurate method for quantitative analysis of natural polysaccharides and their different fractions was developed. Firstly, high performance size exclusion chromatography (HPSEC) was utilized to separate natural polysaccharides. And then the molecular masses of their fractions were determined by multi-angle laser light scattering (MALLS). Finally, quantification of polysaccharides or their fractions was performed based on their response to refractive index detector (RID) and their universal refractive index increment (dn/dc). Accuracy of the developed method for the quantification of individual and mixed polysaccharide standards, including konjac glucomannan, CM-arabinan, xyloglucan, larch arabinogalactan, oat ?-glucan, dextran (410, 270, and 25kDa), mixed xyloglucan and CM-arabinan, and mixed dextran 270K and CM-arabinan was determined, and their average recoveries were between 90.6% and 98.3%. The limits of detection (LOD) and quantification (LOQ) were ranging from 10.68 to 20.25?g/mL, and 42.70 to 68.85?g/mL, respectively. Comparing to the conventional phenol sulfuric acid assay and HPSEC coupled with evaporative light scattering detection (HPSEC-ELSD) analysis, the developed HPSEC-MALLS-RID method based on universal dn/dc for the quantification of polysaccharides and their fractions is much more simple, rapid, and accurate with no need of individual polysaccharide standard, as well as free of calibration curve. The developed method was also successfully utilized for quantitative analysis of polysaccharides and their different fractions from three medicinal plants of Panax genus, Panax ginseng, Panax notoginseng and Panax quinquefolius. The results suggested that the HPSEC-MALLS-RID method based on universal dn/dc could be used as a routine technique for the quantification of polysaccharides and their fractions in natural resources. PMID:25990349

  2. In vitro evaluation of total venom-antivenin immune complex formation and binding parameters relevant to antivenin protection against venom toxicity and lethality based on size-exclusion high-performance liquid chromatography.

    PubMed

    Sanny, Charles G

    2011-05-01

    Total venom-antivenin immune complex formation and binding parameters relevant to antivenin protection against venom toxicity and lethality can be evaluated using size-exclusion high-performance liquid chromatography (SE-HPLC). Simple integration of regions within SE-HPLC elution profiles was used to compare binding characteristics of Crotalidae Polyvalent Immune Fab (Ovine) antivenin (FabAV) and Crotalus atrox (western diamondback rattlesnake; C. atrox), C. varidis varidis (prairie rattlesnake; C. v. v.), Agkistrodon contortrix contortrix (southern copperhead; A. c. c.), and A. piscivorus leukostoma (western cottonmouth; A. p. l.) venom. Areas associated with bound venom and antivenin ({Area(bnd)}) were evaluated using a logistic dose-response equation to estimate EC(50) and {Area(bnd)}(max). The relative magnitudes of EC(50), which inversely reflect venom-antivenin binding affinity, were C. atrox > C. v. v. > A. c. c. > A. p. l. Less than 50% of FabAV appeared to be reactive with each of the venoms based on {Area(bnd)}(max). Data was also consistent with FabAV binding to multiple sites on polyvalent antigens within the venoms. Evaluation of immune complex formation using SE-HPLC was compared to neutralization of phospholipase A(2) (PLA(2)) activity of C. atrox, A. c. c., and A. p. l. venom by FabAV as reported in the literature. Maximum neutralization of PLA(2) activity occurred, in general, prior to maximum immune complex formation. Venom-antivenin binding at EC(50) determined via SE-HPLC appeared to be greater than binding associated with neutralization of venom lethality in mice based on LD(50) and ED(50) reported by others. SE-HPLC analysis of venom-antivenin binding could provide a priori information, relevant to reducing the use of animals in evaluating antivenin protection against venom-induced toxicity and lethality. PMID:21392522

  3. Simultaneous targeted analysis of five active compounds in licorice by ultra-fast liquid chromatography coupled to hybrid linear-ion trap tandem mass spectrometry.

    PubMed

    Kong, Weijun; Wen, Jing; Yang, Yinhui; Qiu, Feng; Sheng, Ping; Yang, Meihua

    2014-04-21

    An ultra-fast liquid chromatography with electrospray ionization tandem mass spectrometry (UFLC-ESI-MS/MS) method was developed for targeted analysis of 5 active compounds in licorice for the first time. The sample preparation procedure, chromatographic and mass spectrographic conditions were optimized. By using a Kinetex C18 100A column, the five compounds were separated within 8.0 min by gradient elution using methanol containing 0.1% acetic acid and 0.1% aqueous acetic acid. The precursor and product ions of the analytes were monitored on a hybrid quadrupole/linear ion trap mass spectrometer equipped with a turbo ion spray interface in negative ionization mode (ESI(-)) and were simultaneously characterized and quantified based on the multiple reaction monitoring-information-dependent acquisition-enhanced product ion (MRM-IDA-EPI) mode. All standard calibration curves expressed satisfactory linearity (r ? 0.9954) within a relatively wide range. The precision was evaluated by intra- and inter-day tests, which revealed relative standard deviation (RSD) values within the ranges of 1.15-4.56% and 0.81-3.95%, respectively. The recovery assays for the quantified compounds were between 97.33 and 100.4% with RSD values less than 4.27%. The proposed method was demonstrated to be simple, rapid, specific and reliable and was successfully applied for identification and quantification of 5 active compounds in 10 batches of licorice. The results showed that the contents of the 5 compounds in licorice from different sources were widely varied. PMID:24551874

  4. Nano-fabricated size exclusion chromatograph

    NASA Technical Reports Server (NTRS)

    Svehla, D.; Feldman, S.; Feldman, J.; Grunthaner, F.; Shakkottai, P.; Castillo, L. del; White, V.

    2002-01-01

    This paper describes the development of a nano-fabricated size exclusion chromatograph (nSEC) based on the principle that molecules traveling through amicrocolumn containing nano-fabricated features will have characteristic elution times that directly correlate to molecular weight. Compared to conventional size exclusion chromatography, the nSEC offers greater control over the size exclusion process; mass fabrication; integration of the separation column with associated valves, pumps, and detectors; and dramatic reductions in instrument mass and power requirements.

  5. [Rapid screening and confirming carcinogenic banned azo colorants in textiles by high performance liquid chromatography-linear ion trap/orbitrap high-resolution mass spectrometry].

    PubMed

    Yun, Huan; Liu, Xin; Wang, Jing; Yan, Hua; Cui, Fengyun; Zhang, Zhaohui

    2013-09-01

    A method of high performance liquid chromatography-linear ion trap/orbitrap highresolution mass spectrometry (HPLC-LTP/Orbitrap MS) was ued to screen and confirm-banned azo colorants in textiles rapidly. The analytes were reduced to carcinogenic aromatic amines with sodium dithionite in citrate buffer solution. The reduced solution was extracted bydiatomite, and loadd onto an Acquity UPLC BEH C18 column (50 mm x 2.1 MM. 1.7 microm) with a gradient elution of methanol and 0.1% (v/v) methane acid aqueous solution, and finally detected by linear ion trap/orbitrap high-resolution mass spectrometry in positive ESI mode. In mass spectrometry method, the MS spectrum of high-resolution and the collision induced dissociation (CID) spectrum of data-dependent scan mode were used for screening analysis and conformation, respectively. The calibration curves showed a good linearity in the range of 0.05 -2.00 mg/b, and the correlation coefficients (r) were higher than 0.99. By detecting spiked samples, the limits of quantification were 0.08 mg/kg for all the residues and the recoveries were in the range of 65.5% - 111.5% with the relative standard deviations (RSDs) between 0.87% and 2.49%. The results indicate that the method is simple, rapid, sensitive and suitable for the qualitative and quantitative analysis of carcinogenic aromatic amines in textiles. PMID:24392621

  6. Quantitative Phosphoproteome Analysis of Lysophosphatidic Acid Induced Chemotaxis applying Dual-step ¹?O Labeling Coupled with Immobilized Metal-ion Affinity Chromatography

    SciTech Connect

    Ding, Shi-Jian; Wang, Yingchun; Jacobs, Jon M.; Qian, Weijun; Yang, Feng; Tolmachev, Aleksey V.; Du, Xiuxia; Wang, Wei; Moore, Ronald J.; Monroe, Matthew E.; Purvine, Samuel O.; Waters, Katrina M.; Heibeck, Tyler H.; Adkins, Joshua N.; Camp, David G.; Klemke, Richard L.; Smith, Richard D.

    2008-10-01

    Reversible protein phosphorylation is a central cellular regulatory mechanism in modulating protein activity and propagating signals within cellular pathways and networks. Development of more effective methods for the simultaneous identification of phosphorylation sites and quantification of temporal changes in protein phosphorylation could provide important insights into molecular signaling mechanisms in a variety of different cellular processes. Here we present an integrated quantitative phosphoproteomics approach and its applications for comparative analysis of Cos-7 cells in response to lysophosphatidic acid (LPA) gradient stimulation. The approach combines trypsin-catalyzed 16O/18O labeling plus 16O/18O-methanol esterification labeling for quantitation, a macro- Immobilized Metal-ion Affinity Chromatography trap for phosphopeptide enrichment, and a monolithic capillary column with integrated electrospray emitter. LC separation and MS/MS is followed by neutral loss-dependent MS/MS/MS for phosphopeptide identification using a linear ion trap (LTQ)-FT mass spectrometer and complementary searching algorithms for interpreting MS/MS spectra. Protein phosphorylation involved in various signaling pathways of cell migration were identified and quantified, such as mitogen-activated protein kinase 1, dual-specificity mitogen-activated protein kinase kinase 2, and dual-specificity tyrosine-phosphorylation regulated kinase 1b, and a number of Rho GTPase-activating proteins. These results demonstrate the efficiency of this quantitative phosphoproteomics approach and its application for rapid discovery of phosphorylation events associated with gradient sensing and cell chemotaxis.

  7. [Determination of fosetyl-aluminium by ion-pair reversed phase-high performance liquid chromatography with evaporative light scattering detection].

    PubMed

    Fan, Zhixian; Jia, Shumin; Ding, Ning; Zhao, Wenying; Wang, Shujuan

    2009-11-01

    Ion-pair reversed phase-high performance liquid chromatography (RP-HPLC) with evaporative light scattering detection (ELSD) has been established for the analysis of fosetyl-aluminium and relevant impurities in technical or formulated substance. The method was achieved on a Symmetry Shield RP18 column by using n-butylamine as ion-pairing agent. The mobile phase was methanol-redistilled water containing 0.5% n-butylamine which was adjusted pH 5.0 with acetic acid (8:92, v/v) and the flow rate was set at 0.8 mL/min. The active ingredient fosetyl-aluminium was successfully separated from relevant impurities under the conditions. The calibration curve was linear in the range of 100-1200 mg/L. The average recoveries of two fortification levels (100 mg/L and 1000 mg/L) were 100.58% and 99.53%, and the relative standard deviations (RSDs) were 0.62% and 0.49%, respectively. The method is rapid, simple and accurate which provides another new and reliable means for the analysis of fosetyl-aluminium in its technical or formulated substance. PMID:20352944

  8. Monitoring of phosphorus oxide ion for analytical speciation of phosphite and phosphate in transgenic plants by high-performance liquid chromatography-inductively coupled plasma mass spectrometry.

    PubMed

    Torres Elguera, Julio Cesar; Yañez Barrientos, Eunice; Wrobel, Katarzyna; Wrobel, Kazimierz

    2013-07-10

    Large amounts of phosphate fertilizers utilized in agriculture and their relatively poor efficiency are of high ecological and economic concern. Therefore, transgenic plants capable of metabolizing phosphite are being engineered. In support of this biotechnological task, analytical speciation of phosphorus in biological tissues is required. In this study, plant extracts were analyzed by liquid chromatography-inductively coupled plasma mass spectrometry at m/z of elemental phosphorus and phosphorus oxide ions. Using polymeric-based anion exchange column and millimolar concentration of nitric acid in potassium phthalate mobile phase (pH 2.5), phosphite and phosphate ions were baseline resolved with retention times 6.95 ± 0.03 and 7.90 ± 0.03 min and with a total chromatographic run time 10 min. The detection limits were 1.58 and 1.74 ?g P L(-1) at m/z 47, as compared to 2.18 and 2.04 ?g P L(-1) at m/z 31, respectively. The results obtained in real world samples for the two detection modes were in good agreement, yet signal acquisition at m/z 47 enabled better precision without collision/reaction cell (RSD below 2%) as compared to RSD around 4% obtained at m/z 31 using He-pressurized cell (3.5 mL min(-1)). PMID:23782169

  9. Localization of double bonds in triacylglycerols using high-performance liquid chromatography/atmospheric pressure chemical ionization ion-trap mass spectrometry.

    PubMed

    Háková, Eva; Vrkoslav, Vladimír; Míková, Radka; Schwarzová-Pecková, Karolina; Bosáková, Zuzana; Cva?ka, Josef

    2015-07-01

    A method for localizing double bonds in triacylglycerols using high-performance liquid chromatography-tandem mass spectrometry with atmospheric pressure chemical ionization (APCI) was developed. The technique was based on collision-induced dissociation or pulsed Q collision-induced dissociation of the C3H5N(+•) adducts ([M + 55](+•)) formed in the presence of acetonitrile in the APCI source. The spectra were investigated using a large series of standards obtained from commercial sources and prepared by randomization. The fragmentation spectra made it possible to determine (i) the total number of carbons and double bonds in the molecule, (ii) the number of carbons and double bonds in acyls, (iii) the acyl in the sn-2 position on the glycerol backbone, and (iv) the double-bond positions in acyls. The double-bond positions were determined based on two types of fragments (alpha and omega ions) formed by cleavages of C-C bonds vinylic to the original double bond. The composition of the acyls and their positions on glycerol were established from the masses and intensities of the ions formed by the elimination of fatty acids from the [M + 55](+•) precursor. The method was applied for the analysis of triacylglycerols in olive oil and vernix caseosa. Graphical Abstract The diagnostic fragments in the APCI PQD MS(2) spectrum of the [M + 55](+•) adduct of triolein. PMID:25701424

  10. Isomerism of [64Cu-NOTA-Bn]-labeled radiotracers: separation of two complex isomers and determination of their interconversion energy barrier using ion pair chromatography.

    PubMed

    Schlesinger, Joern; Rajander, Johan; Ihalainen, Janne A; Ramesh, Dinesh; Eklund, Patrik; Fagerholm, Veronica; Nuutila, Pirjo; Solin, Olof

    2011-05-16

    The model complex [(64)Cu((S)-p-NH(2)-Bn-NOTA)](-) ([(64)Cu]1) was used to study the isomerism of [(64)Cu-NOTA-Bn]-labeled radiotracers. Two complex isomers [(64)Cu]1a and [(64)Cu]1b, which were formed at a ratio of 1:9 during the complexation of [(64)Cu]Cu(2+) with (S)-p-NH(2)-Bn-NOTA, were separated using ion pair chromatography. To study the interconversion, the nonradioactive complex isomers Cu1a and Cu1b were separated and thermally treated at 90 °C in both ammonium acetate solution and deionized water. A faster interconversion rate was observed for both isomers with lower concentrations of ammonium ions. At the end of reaction, the thermodynamic Cu1a to Cu1b equilibrium ratio was 6:94. The particular energy barriers of the interconversion for Cu1a and Cu1b were 130 kJ mol(-1) and 140 kJ mol(-1). Spectrophotometric measurements with Cu1a and Cu1b revealed two isomers adopting different geometrical configurations. PMID:21488661

  11. Development of online sampling and matrix reduction technique coupled liquid chromatography/ion trap mass spectrometry for determination maduramicin in chicken meat.

    PubMed

    Chang, Kai Chun; Su, Jung Jeng; Cheng, Cheanyeh

    2013-11-15

    An online sampling and matrix reduction technique coupled liquid chromatography electrospray-ion-trap mass spectrometry was developed for rapid analysis of maduramicin (MAD) residue in chicken meat. Multiple-reaction monitoring of mass spectrometry in positive ion mode was used to detect maduramicin. A post-column continuous infusion of internal standard (nigericin) with matrix-matched calibration method was utilised for quantification. The linear concentration range of the calibration curve was 0-10.0 ng mL(-1) (r(2)=0.999). The limit of detection (quantification) was 0.08 ng g(-1) (0.28 ng g(-1)). The analytical accuracy of chicken meat samples for four spiked MAD concentrations (0.5, 1.0, 5.0, and 10.0 ng g(-1)) was 84-97% and their corresponding intra-day and inter-day precisions were 3.7-5.0% and 5.8-7.9%, respectively. The analysis time for one sample was 10 min. The application of the method for incurred chicken samples elucidates that MAD residue in chicken meat decreases during the withdrawal period. PMID:23790947

  12. Chemical analysis of uranium and titanium niobotantalate metamict minerals by ion-exchange chromatography and spectrophotometric procedures.

    PubMed

    Mazzucotelli, A; Vannucci, R; Vannucci, S; Passaglia, E

    1984-03-01

    An ion-exchange separation followed by spectrophotometric determinations is applied to some metamict minerals. These minerals, containing very high amounts of elements which present some problems to the analyst, such as uranium, titanium, niobium and rare-earth elements, are fused with potassium bisulphate, and the cooled melts dissolved in sulphuric acid. The solutions are passed through a series of three ion-exchange columns to separate those mineral-forming elements for which the colorimetric procedures suffer interference from the elements listed above. The procedure has been tested with a synthetic solution and with solutions of the minerals. PMID:18963564

  13. Dynamic behavior of binary component ion-exchange displacement chromatography of proteins visualized by confocal laser scanning microscopy.

    PubMed

    Shi, Qing-Hong; Shi, Zhi-Cong; Sun, Yan

    2012-09-28

    Confocal laser scanning microscopy (CLSM) was introduced to visualize particle-scale binary component protein displacement behavior in Q Sepharose HP column. To this end, displacement chromatography of two intrinsic fluorescent proteins, enhanced green fluorescent protein (eGFP) and red fluorescent protein (RFP), were developed using sodium saccharin (NaSac) as a displacer. The results indicated that RFP as well as eGFP could be effectively displaced in the single-component experiments by 50 mmol/L NaSac at 120 and 140 mmol/L NaCl whereas a fully developed displacement train with eGFP and RFP was only observed at 120 mmol/L NaCl in binary component displacement. At 140 mmol/L NaCl, there was a serious overlapping of the zones of the two proteins, indicating the importance of induced-salt effect on the formation of an isotachic displacement train. CLSM provided particle-scale evidence that induced-salt effect occurred likewise in the interior of an adsorbent and was synchronous to the introduction of the displacer. CLSM results at 140 mmol/L NaCl also demonstrated that both the proteins had the same fading rate at 50 mmol/L NaSac in the initial stage, suggesting the same displacement ability of NaSac to both the proteins. In the final stage, the fading rate of RFP in the adsorbent became slow, particularly at lower displacer concentrations. In the binary component displacement, the two proteins exhibited distinct fading rates as compared to the single component displacement and the remarkable lagging of the fading rate was observed in protein displacements. It suggested that the co-adsorbed proteins had significant influence on the formation of an isotachic train and the displacement chromatography of the proteins. Therefore, this research provided particle-scale insight into the dynamic behavior and complexity in the displacement of proteins. PMID:22901622

  14. Simultaneous determination of copper(II) and cobalt(II) by ion chromatography coupled with chemiluminescent detection.

    PubMed

    Lu, Chao; Lin, Jin-Ming; Huie, Carmen W; Yamada, Masaaki

    2003-04-01

    In the absence of any special luminescent reagents, a weakly chemiluminescent emission was observed during the decomposition of hydrogen peroxide, catalyzed by transition-metal ions, such as Cu(II) and Co(II), in basic aqueous solution. The chemiluminescent intensity was significantly enhanced by the addition of ethyldimethylcetylammonium bromide and uranine. The signal-to-noise ratio (S/N) was proportional to the concentrations of Cu(II) and Co(II). Based on these phenomena, a flow-injection chemiluminescent method for the simultaneous separation and determination of Cu(II) and Co(II) was developed. The detection limits of the present chemiluminescent method for Cu(II) and Co(II) were 7.5 and 0.01 ng/ml, respectively. After ion chromatographic separation of Cu(II) and Co(II) by an IonPac CS5A column with oxalic acid and lithium hydroxide monohydrate as the eluent, the present chemiluminescent system was used as a post-column detector for these two transition metal ions in natural water samples. PMID:12725391

  15. Qualitative Metabolome Analysis of Human Cerebrospinal Fluid by 13C-/12C-Isotope Dansylation Labeling Combined with Liquid Chromatography Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Guo, Kevin; Bamforth, Fiona; Li, Liang

    2011-02-01

    Metabolome analysis of human cerebrospinal fluid (CSF) is challenging because of low abundance of metabolites present in a small volume of sample. We describe and apply a sensitive isotope labeling LC-MS technique for qualitative analysis of the CSF metabolome. After a CSF sample is divided into two aliquots, they are labeled by 13C-dansyl and 12C-dansyl chloride, respectively. The differentially labeled aliquots are then mixed and subjected to LC-MS using Fourier-transform ion cyclotron resonance mass spectrometry (FTICR MS). Dansylation offers significant improvement in the performance of chromatography separation and detection sensitivity. Moreover, peaks detected in the mass spectra can be readily analyzed for ion pair recognition and database search based on accurate mass and/or retention time information. It is shown that about 14,000 features can be detected in a 25-min LC-FTICR MS run of a dansyl-labeled CSF sample, from which about 500 metabolites can be profiled. Results from four CSF samples are compared to gauge the detectability of metabolites by this method. About 261 metabolites are commonly detected in replicate runs of four samples. In total, 1132 unique metabolite ion pairs are detected and 347 pairs (31%) matched with at least one metabolite in the Human Metabolome Database. We also report a dansylation library of 220 standard compounds and, using this library, about 85 metabolites can be positively identified. Among them, 21 metabolites have never been reported to be associated with CSF. These results illustrate that the dansylation LC-FTICR MS method can be used to analyze the CSF metabolome in a more comprehensive manner.

  16. Comprehensive Two-Dimensional Separation of Hydroxylated Polybrominated Diphenyl Ethers by Ultra-Performance Liquid Chromatography Coupled with Ion Mobility-Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Ma, Qiang; Wang, Chao; Bai, Hua; Xi, Hai-Wei; Xi, Guang-Cheng; Ren, Xiao-Min; Yang, Yu; Guo, Liang-Hong

    2011-10-01

    A comprehensive two-dimensional system coupling ultra-performance liquid chromatography (UPLC) and ion mobility-mass spectrometry (IM-MS) has been applied for the separation and analysis of hydroxylated polybrominated diphenyl ethers (OH-PBDEs). A complex mixture containing 23 OH-PBDE congeners ranging from hydroxylated monobromodiphenyl ether (OH-monoBDE) to hydroxylated octabromodiphenyl ether (OH-octaBDE) was satisfactorily separated within 16 min of analysis time. The first-dimensional reversed-phase UPLC was performed on a sub-2 ?m BEH C18 chromatographic column using acetonitrile-water gradient elution program with a flow rate ramp. It enabled excellent chromatographic separation for both between-class and within-class OH-PBDEs based on their differences in hydrophobicity. Following the pre-ionization resolution in the first dimension, the second-dimensional IM-MS employed a hybrid electrospray quadrupole ion mobility time-of-flight mass spectrometer and added an extra post-ionization separation for between-class OH-PBDE congeners on account of their relative mobility disparity during a very short period of 8.80 ms. The orthogonality of the developed two-dimensional system was evaluated with the correlation coefficient of 0.9665 and peak spreading angle of 14.87°. The peak capacity of the system was calculated to be approximately 2 and 15 times higher than that of the two dimensions used alone, respectively. The two-dimensional separation plane also contributed to the removal of background interference ions and the enhanced confidence in the characterization of OH-PBDEs of interest.

  17. Structural evaluation of the glucuronides of morphine and formoterol using chemical derivatization with 1,2-dimethylimidazole-4-sulfonyl chloride and liquid chromatography/ion trap mass spectrometry.

    PubMed

    Salomonsson, Matilda Lampinen; Bondesson, Ulf; Hedeland, Mikael

    2008-09-01

    For the first time chemical derivatization of isomeric drug glucuronides with 1,2-dimethylimidazole-4-sulfonyl chloride (DMISC) has been successfully applied as a tool for determining the site of conjugation. This provides a way to differentiate between glucuronide isomers containing aliphatic and phenolic hydroxyl groups. The analyses were performed with liquid chromatography/electrospray ion trap mass spectrometry (LC/ESI-MSn). DMISC has previously been shown to react selectively with phenols in estrogens, thus improving sensitivity in ESI-MS. The model compounds selected for this study were commercially available standards of formoterol, morphine, morphine-3-glucuronide (M3G), and morphine-6-glucuronide (M6G). Formoterol glucuronides were produced with an enzymatic method in house. Both formoterol and morphine possess one phenolic and one aliphatic hydroxyl group where glucuronidation could take place. The product ion mass spectra of the native morphine glucuronides were indistinguishable due to the initial neutral loss of monodehydrated glucuronic acid (176 u). However, a significant difference between the isomers was observed with DMISC derivatization, as only the form with a free phenol, M6G, gave a detectable reaction product. Formoterol formed two detectable glucuronide isomers in the enzymatic reaction. Their respective sites of conjugation could not be directly determined from the product ion spectra. Reaction with DMISC, however, gave a detectable product with only one of the isomers. Based on previous experience of the preferred DMISC reactions with phenols, and interpretation of the fragmentation pattern of the derivative, it was concluded that the reactive isomer had a free phenol, and was thus conjugated on the aliphatic chain. PMID:18677706

  18. Optimization of electrospray interface and quadrupole ion trap mass spectrometer parameters in pesticide liquid chromatography/electrospray ionization mass spectrometry analysis.

    PubMed

    Kruve, Anneli; Herodes, Koit; Leito, Ivo

    2010-04-15

    Optimization of both the ionization process and ion transportation in the mass spectrometer is of crucial importance in order to achieve high sensitivity and low detection limits and acceptable accuracy in liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) analysis. In this paper four optimization procedures of electrospray interface and quadrupole ion-trap mass spectrometer parameters (ESI-MS) (nebulizer gas and drying gas flow rate, end plate voltage, capillary voltage, skimmer voltage, octopoles direct current and radio frequency, trap drive and lens voltages) were studied on three pesticides--thiabendazole, aldicarb and imazalil. The results demonstrate that the methodology of optimization strongly influences the effectiveness of finding true optima of the operating parameters. Both eluent flow rate and composition during optimization have to mimic the situation during real analysis as closely as possible in order to achieve parameters giving the highest sensitivity. Therefore, post-column addition of analyte to the mobile phase identical in composition to the one in which analyte elutes during real analysis combined with software-based optimization was found to be the most effective and fastest method for achieving intensity maxima. The parameters most strongly affecting ion formation and transportation, hence sensitivity, were capillary voltage, direct current of the first octopole, trap drive and the second lens for all pesticides under study. In addition to sensitivity and detection limit matrix effect was considered in the optimization process. It was found that the matrix effect can be reduced but not eliminated by adjusting the ESI and MS parameters. The optimal parameters from the point of view of the matrix effect can only be found with factorial design. Parameters giving higher sensitivity tended to be more affected by matrix effect causing higher ionization suppression by co-eluting compounds. PMID:20196177

  19. Ion-paired extraction of cephalosporins in acetone prior to their analysis by capillary liquid chromatography in environmental water and meat samples.

    PubMed

    Quesada-Molina, Carolina; García-Campaña, Ana M; del Olmo-Iruela, Monsalud

    2013-10-15

    Ion-pair extraction of cephalosporins from aqueous solution into acetone by the addition of ammonium sulfate to a 1:2 (v/v) acetone-water solvent was carried out followed by their determination using reversed-phase capillary liquid chromatography. The analytes included are cephoperazone, cefquinome, cephalexin, cephapirin, cephaloniun, cephamandole, cephazolin and cephadroxile. In order to form the ion-pair, hexadecyltrimethylammonium bromide (CTAB) was selected as cationic ion-pairing agent at a concentration of 0.9 mM using 10mM phosphate buffer at pH 8 as the optimum condition for the aqueous solution. The applied methodology, named salting-out assisted liquid/liquid extraction (SALLE) involves the use of 1.25 g of ammonium sulfate as salting-out agent. The separation of cephalosporins using a Luna C18 (150 mm × 0.3mm, 5 µm, 100 Å) column was achieved under the following conditions: a gradient program combining solvent A (0.1% formic acid in water, pH 4) and solvent B (acetonitrile-methanol (50:50, v/v)), at a flow rate of 20 µl min(-1), column temperature 35°C and injection volume 7 µl with UV detection at 250 nm. The limits of quantification for the studied compounds were between 4.3 and 22.7 ?g/L for water samples and 4.1 and 73.3 ?g/kg in the case of beef samples, lower than the maximum residue limits permitted by the EU for this kind of food. The developed methodology has demonstrated its suitability for the analysis of these widely applied antibiotics in environmental water and meat samples, including beef and pork muscle, with high sensitivity, precision and satisfactory recoveries. PMID:24054686

  20. Exclusive muon-pair production in ultrarelativistic heavy-ion collisions: Realistic nucleus charge form factor and differential distributions

    SciTech Connect

    Klusek-Gawenda, M. [Institute of Nuclear Physics PAN, PL-31-342 Cracow (Poland); Szczurek, A. [Institute of Nuclear Physics PAN, PL-31-342 Cracow (Poland); University of Rzeszow, PL-35-959 Rzeszow (Poland)

    2010-07-15

    The cross sections for exclusive muon-pair production in nucleus-nucleus collisions are calculated and several differential distributions are shown. Realistic (Fourier transform of charge density) charge form factors of nuclei are used and the corresponding results are compared with the cross sections calculated with monopole form factor often used in the literature and discussed recently in the context of higher-order QED corrections. Absorption effects are discussed and quantified. The cross sections obtained with realistic form factors are significantly smaller than those obtained with the monopole form factor. The effect is bigger for large muon rapidities and/or large muon transverse momenta. The predictions for the STAR and PHENIX collaboration measurements at RHIC as well as the ALICE and CMS collaborations at LHC are presented.

  1. Ion-pair reversed-phase chromatography of short double-stranded deoxyribonucleic acid in silicon micro-pillar array columns: retention model and applications.

    PubMed

    Zhang, Lei; Majeed, Bivragh; Lagae, Liesbet; Peumans, Peter; Van Hoof, Chris; De Malsche, Wim

    2013-06-14

    Separation of double-stranded (ds) DNAs is important in numerous biochemical analyses relevant for clinical applications. A widely used separation technique is high performance liquid chromatography (HPLC), in the variant of ion-pair reversed-phase (IP-RP) chromatography. HPLC can be miniaturized by means of silicon micro-pillar array columns leading to on-chip fast and high resolution dsDNA separation with limited sample quantity. However, theoretical studies of retentive behavior of dsDNA in miniaturized chromatographic columns are hardly available, despite their enormous practical relevance. This paper established a new retention model to describe the size dependent separation of dsDNAs for any characteristic of the linear mobile phase gradient, in analogy to the model used to describe the retention of polymer chains with repeating units in RP HPLC. The model agrees with a large amount of dsDNA retention data, measured using DNA molecules in the size range of 10-400 base pairs in columns with different lengths (2 and 40cm) and different micro-pillar sizes (2 and 2.5?m in diameter), in various mobile phase gradients. The model is particularly useful in practice, since it requires no numerical solutions and the column-specific fitting parameters (4 or 5) can be determined in a limited number of separation runs. As examples of its applications, the model has been used for the optimization of dsDNA step-gradient separations (5 dsDNAs separated within 8min) and for the determination of the size of dsDNA fragment (with uncertainty of about 2%). These applications are especially relevant for on-chip DNA analysis devices. PMID:23647613

  2. Quantitative analysis in gas chromatography/low power atmospheric-pressure helium microwave-induced plasma atomic emission interferometry and ion cyclotron resonance mass spectroscopy

    SciTech Connect

    Loo, J.F.

    1990-01-01

    The development of experimental and data analysis techniques for quantitative analysis in gas chromatography/low power atmospheric pressure helium microwave-induced plasma atomic emission interferometry (GC/HeMIPAEI) and ion cyclotron resonance mass spectroscopy (ICR/MS) is presented. A discussion of interferometric data analysis by discrete and fast Fourier transform (DFT and FFT, respectively) is given. Additionally, the use of two techniques (the maximum entropy method, or MEM, and linear prediction, or LP) that have shown to produce results superior to those from the FFT is shown for synthetic and experimental NMR, optical, and mass spectral data. Visual spectral comparisons, performance results as compared to known spectral parameters, and a methodology for the implementation of the linear prediction technique is given. A low-power HeMIP was constructed and used as the excitation source for an AEI detector for gas chromatography. In general, HeMIPs have the advantage of being able to excite non-metal atoms, which comprise a large fraction of the molecules used in typical organic GC analysis. Sensitivity, detection limits, their dependence on microwave power values, and elemental emission ratios are tabulated for a series of test compounds. Results show that elemental emission ratios are independent of the structure of the compound used in this study. Suggestions for further development, from the use of a concentric-flow torch and optical filters to the removal of oxygen through the use of ultra-high purity helium, are presented. Through the use of coherent pulsed excitation, electronic quadrature detection, and data analysis by linear prediction, ICR/MS relative abundance error values for the principal isotopes of krypton have been calculated to be less than 1%.

  3. Characterization of a rapid and reliable method for iodide biomonitoring in serum and urine based on ion chromatography-ICP-mass spectrometry.

    PubMed

    Michalke, Bernhard; Witte, Heidi

    2015-01-01

    An appropriate and controlled supply of thyroid hormones is vital for proper body function. In turn, an appropriate synthesis of T3 and T4 in the thyroid gland is dependent on a sufficient and balanced iodide concentration in blood serum. Due to widespread iodine deficiency or some cases of iodine over exposure, iodide biomonitoring in serum is important and it is that biomonitoring approach being closest to the bioavailable I(-) supply for the thyroid gland. Therefore, this paper describes a biomonitoring method for iodide determination in serum based on ion chromatography-inductively coupled plasma mass spectrometry (IC-ICP-MS). Since in literature only very few data are available on iodide in serum but many in urine the method is also extended to I(-) monitoring in urine. The method was additionally designed to have short analysis time (8min) for increased sample throughput, good precision in serial measurement (serum: 4.86%; urine: 1.4%), and day-to-day determination (serum: 5.7%; urine: 2.28%), high accuracy (serum: 105%; urine: 101%) and good recovery (serum: 102%; urine: 99%) even in matrix-rich samples at low I(-) concentration. Also, investigations were performed to elucidate whether internal standardization during chromatography, sample preparation for protein-matrix removal or matrix-matched calibration are advantageous for analytical performance. Finally, limits of detection (3?) of 0.12?g/L or 0.05?g/L (serum or urine) and limit of quantification (10?) of 0.39?g/L or 0.17?g/L (serum or urine) were achieved. PMID:24933092

  4. Detection of carbohydrates by electrospray ionization-ion mobility spectrometry following microbore high-performance liquid chromatography

    Microsoft Academic Search

    Dong-Sun Lee; Ching Wu; Herbert H. Hill

    1998-01-01

    This paper reports the first example of electrospray ion mobility spectrometry as a detection method for HPLC separation, demonstrating its potential for the quantitative and selective detection of non-volatile and non-chromophoric organic compounds. Reduced mobility constants (K0) for 21 carbohydrates, including simple sugars, sugar alcohols and amino sugars, were determined to range from 0.68 to 1.37 cm2 V?1 s?1. Minimum

  5. Express analysis of explosives, chemical warfare agents and drugs with multicapillary column gas chromatography and ion mobility increment spectrometry

    Microsoft Academic Search

    Igor A. Buryakov

    2004-01-01

    Description of a gas chromatograph designed for express analysis of explosives (2,4-dinitrotoluene, 2,4,6-trinitrotoluene, pentaerythritol tetranitrate), chemical warfare agents (mustard gas, lewisite, sarin) and drugs (heroin, cocaine hydrochloride, crack) is given. The devices comprises a multicapillary chromatographic column and an ion mobility increment spectrometer (MCC–IMIS). The main analytical characteristics of an IMIS (estimated detection limit (DL), linear dynamic range (LDR), speed

  6. Determination of testosterone and epitestosterone glucuronides in urine by ultra performance liquid chromatography-ion mobility-mass spectrometry.

    PubMed

    Kaur-Atwal, Gushinder; Reynolds, James C; Mussell, Christopher; Champarnaud, Elodie; Knapman, Tom W; Ashcroft, Alison E; O'Connor, Gavin; Christie, Steven D R; Creaser, Colin S

    2011-10-01

    UPLC-ion mobility spectrometry separations combined with mass spectrometry (UPLC-IM-MS) and tandem mass spectrometry (UPLC-IM-MS/MS) have been investigated for the simultaneous determination of testosterone and epitestosterone glucuronides in urine. The glucuronide epimers of testosterone and epitestosterone were separated by ion mobility spectrometry prior to mass analysis on the basis of differences in their collision cross sections, which have been measured in nitrogen. Combining ion mobility separation with UPLC/MS enhances the analysis of these low-abundance steroids in urine by selective interrogation of specific retention time, mass-to-charge and mobility regions. Detection limits for the UPLC-IM-MS/MS analysis of TG and ETG were 9.9 ng mL(-1) and 98 ng mL(-1) respectively, equivalent to 0.7 ng mL(-1) and 7.4 ng mL(-1) in urine, with linear dynamic ranges corresponding to 0.7-108 ng mL(-1) and 7.4-147 ng mL(-1) in urine. Repeatability (%RSD) for urine extracts was 0.64% and 2.31% for TG and ETG respectively. PMID:21842047

  7. Fractal calibration in size-exclusion chromatography

    Microsoft Academic Search

    Rosa Garc??a-Lopera; Isabel Irurzun; Concepción Abad; Agust??n Campos

    2003-01-01

    The elution behaviour of different polymer–solvent systems in three types of organic columns for SEC has been compared and interpreted. The experimental data show that the classical universal calibration is not accomplished. Deviations from a unique curve are observed due to the binary and ternary interactions between the components of the system (solvent, polymer and gel) which results on secondary

  8. A Calibration Technique for Size Exclusion Chromatography

    Microsoft Academic Search

    R. D. Hester; P. H. Mitchell

    1984-01-01

    A modified Weibull distribution function is shown to be useful in calibrating the molecular size separation capabilities of both rigid and swellable gel packing materials. Two parameters are used in this function which are related to a packing material's micropore volume distribution. The calibration curves of a set of different packing materials connected in series were predicted from the Weibull

  9. Determination of nivalenol and deoxynivalenol in wheat using liquid chromatography-mass spectrometry with negative ion atmospheric pressure chemical ionisation.

    PubMed

    Razzazi-Fazeli, E; Böhm, J; Luf, W

    1999-08-27

    A new, rapid and sensitive method has been developed for the determination of nivalenol (NIV) and deoxynivalenol (DON) by using HPLC in combination with an atmospheric pressure chemical ionization (APCI)-interface and a single quadrupole mass spectrometer. Different LC and MS parameters have been optimized prior to this in order to obtain better results and sensitivity. The effect of nebulizing temperature on the sensitivity and fragmentation of NIV and DON in an APCI interface was investigated. Also, the influence of the cone voltage on the fragmentation pattern was studied, which was shown to have a tremendous effect. Furthermore, the effect of modifiers such as ammonium acetate, acetic acid and ammonia on the ionisation yield of the above substances have been investigated. The extraction was carried out using acetonitrile-water. A two step purification was then applied on two different Mycosep clean up columns. We have used a modified, rapid and isocratic HPLC method combined with a negative ion APCI-MS for the separation and quantitative determination of NIV and DON in wheat extract. An RP C18 column was used for the separation of selected compounds in wheat extract with water-acetonitrile-methanol (82:9:9, v/v/v) at a flow-rate of 1 ml/min without a split. Calibration curves show good linearity and reproducibility. The detection limit and precision were determined for NIV and DON. Both compounds could be detected down to microg/kg level in wheat using selected ion monitoring of the [M-H]- ions and the main fragments. PMID:10497927

  10. Column Chromatography

    NSDL National Science Digital Library

    Julie Yu

    2007-01-01

    In this activity, learners separate the components of Gatorade using a home-made affinity column. In doing so, learners model the basic principle of affinity chromatography, a technique used to purify chemicals as well as bio-pharmaceuticals and petroleum products. This resource contains information about affinity chromatography and polarity.

  11. Fast protein liquid chromatography.

    PubMed

    Madadlou, Ashkan; O'Sullivan, Siobhan; Sheehan, David

    2011-01-01

    Fast protein liquid chromatography (FPLC) is a form of high-performance chromatography that takes advantage of high resolution made possible by small-diameter stationary phases. It was originally developed for proteins and features high loading capacity, biocompatible aqueous buffer systems, fast flow rates, and availability of stationary phases in most common chromatography modes (e.g., ion exchange, gel filtration, reversed phase, and affinity). The system makes reproducible separation possible by incorporating a high level of automation including autosamplers, gradient program control, and peak collection. In addition to proteins, the method is applicable to other kinds of biological samples including oligonucleotides and plasmids. The most common type of FPLC experiment is anion exchange of proteins. This chapter describes such an experiment carried out using an ÄKTA FPLC explorer system (Amersham Pharmacia Biotech, Sweden). PMID:20978981

  12. Determination of linear alkylbenzenesulfonates and their degradation products in water samples by gas chromatography with ion-trap mass spectrometry.

    PubMed

    Ding, W H; Lo, J H; Tzing, S H

    1998-09-01

    A method was developed for the analysis of linear alkylbenzenesulfonates (LAS) and their degradation products, sulfophenylcarboxylic acids (SPC), in samples of sewage effluent and river water. This method involved extraction of the samples by graphitized carbon black cartridge, esterification by a two-step thionyl chloride-trifluoroethanol derivatization procedure, and separation, identification and quantitation by ion-trap GC-MS with EI and low pressure CI modes. High selectivity with few signals was observed in the low pressure CI mass spectra of LAS and SPC. Enhanced sensitivity with protonated molecular ion chromatograms of homologous C10-C13 LAS by CI-MS permit the determination of LAS and SPC at trace concentrations in environmental samples. Recovery rates of LAS and SPC in spiked water samples ranged from 75 to 112% with R.S.D. values from 3 to 26%. The limit of quantitation for both LAS and SPC was estimated to be 0.01 microgram/l in 100 ml of water sample. PMID:9770311

  13. Gas chromatography negative ion chemical ionization mass spectrometry: application to the detection of alkyl nitrates and halocarbons in the atmosphere.

    PubMed

    Worton, David R; Mills, Graham P; Oram, David E; Sturges, William T

    2008-08-01

    Alkyl nitrates and very short-lived halocarbon species are important atmospheric trace gas species that are present in the low to sub parts per trillion concentration range. This presents an analytical challenge for their detection and quantification that requires instrumentation with high sensitivity and selectivity. In this paper, we present a new in situ gas chromatograph negative ion chemical ionization mass spectrometer (GC/NICI-MS) coupled to a non-cryogen sample pre-concentration system. This instrument, with detection limits of <0.01 ppt, is capable of detecting and quantifying a large suite of alkyl nitrate and halocarbon species with high sensitivity and precision. The effects of ion source temperature and reagent gas pressure on the ionization efficiency of the NICI mode are investigated and the results are used to optimize the sensitivity. The NICI mode is compared to the more frequently used electron impact (EI) ionization and the enhancements in sensitivity are presented for all the calibrated compounds. PMID:18586255

  14. Separation and detection of ammonia, amines, and alkanolamines with single-column ion chromatography. [Alkylamines, ethanolamine and methyldiethanolamine

    SciTech Connect

    Poulson, R.E.; Borg, H.M.

    1986-03-01

    A single-column ion chromatographic method was developed for separation and detection of aqueous ammonia, C/sub 1/-, C/sub 2/-, and C/sub 3/- alkylamines, ethanolamine, and methyldiethanolamine. A precolumn concentrator was used to take detection of ammonium ion by electrical conductivity to fractional ppB levels and detection of the organic cations to ppB levels. Analysis of ppM ammonia levels in 3 wt % alkanolamine scrubber-type solutions was possible, but resolution of alkylamines was lost. A post-column reaction system for fluorescence detection of primary amine o-phthalaldehyde derivatives with reversed-phase separation allowed amine separation in the presence of large amounts of ammonia. The same system might be used in place of concentration and conductivity for determination of the alkylamine levels. A large variety of oil shale retort by-product waters and one underground coal gasification condensate were screened for alkylamines, but none were detected. 7 refs., 8 figs., 1 tab.

  15. [Determination of beta2-agonists and beta-blockers in urine using high performance liquid chromatography-ion trap mass spectrometry].

    PubMed

    Miao, Hong; Zou, Jianhong; Fan, Sai; Gan, Lewen; Zhao, Yunfeng; Wu, Yongning

    2010-06-01

    A method has been developed for the determination of 23 beta2-agonists and 5 beta-blockers in urine samples using high performance liquid chromatography-ion trap mass spectrometry (HPLC-IT-MS). Urine samples were first deproteinized by high-speed frozen centrifugation, and the supernatants were loaded on an Extrelut diatomite column for clean-up. The analytes were eluted by ethyl acetate and concentrated for further analysis. The analytical separation was performed on an AtlantisT3-150 mm chromatographic column with the gradient elution using methanol and water (containing 0.1% formic acid). The detection was carried on a linear ion trap mass spectrometer under multiple reaction monitoring (MRM) mode with the source operated in positive mode of electrospray ionization (ESI+). Nine deuterium labeled beta2-agonists were used as internal standards for quantitative analysis. The results showed that the linear ranges for 23 beta2-agonists and 5 beta-blockers were 0.005-0.16 mg/L, and the limits of detection were all around 0.2 microg/L. The mixed standard solution was added into the blank urine samples, and the recoveries of 23 beta2-agonists and 5 beta-blockers were ranged from 57.1% to 127.7% with the relative standard deviations of 1.1%-31.1%. The results demonstrate that the method is easy, fast, sensitive, and suitable for the confirmation and quantification of 23 beta2-agonists and 5 beta-blockers in urine samples. PMID:20873578

  16. Liquid chromatography-negative ion atmospheric pressure photoionization tandem mass spectrometry for the determination of brominated flame retardants in environmental water and industrial effluents.

    PubMed

    Bacaloni, Alessandro; Callipo, Luciano; Corradini, Eleonora; Giansanti, Piero; Gubbiotti, Riccardo; Samperi, Roberto; Laganà, Aldo

    2009-09-01

    We describe the development of a liquid chromatography with negative-ion atmospheric pressure photoionization tandem mass spectrometric (LC/NI-APPI/MS/MS) method for the simultaneous determination of tetrabromobisphenol A (TBBP-A) and five polybrominated diphenyl ethers (BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154) in water. A mobile phase methanol/acetone/water was used, where acetone acts also as dopant. NI-APPI produced precursor ions corresponding to [M-H](-) for TBBP-A, [M-Br+O](-), and [M-2Br+O](-) for the BDE congeners studied. Each compound was quantified operating in multiple reaction monitoring mode. Linearity was observed in the range 0.025-10 ng injected for all compounds. Coefficients of determination R(2) ranged from 0.9934 to 0.9982. BDEs were poorly retained by solid-phase extraction (SPE) from river water and sewage treatment plant effluent, thus liquid-liquid extraction (LLE) by n-hexane should be used for these samples. The recoveries of TBBP-A and PBDEs from tap water (SPE), river water and industrial wastewater (LLE) were in the range of 81-88%, 78-92%, and 43-99%, respectively, with relative standard deviations below 17%. The limits of detection, based on signal-to-noise ratio of 3, ranged from 0.004 to 0.1 ng injected, and method quantification limits were 0.2-3.3 ng L(-1) but BDE47 (20.3 ng L(-1)). Only TBBP-A was found in a treated industrial sewage at 4 ng L(-1), while BDE-99 and BDE-100 were detected on suspended solids. PMID:19656519

  17. [Identification of banned aromatic amines and their isomers in textiles by ultra-performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry].

    PubMed

    Ye, Xiwen; Peng, Yan; Niu, Zengyuan; Gao, Yonggang; Luo, Xin; Zou, Li; Zhou, Minghui

    2014-09-01

    A method of ultra-performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry (UPLC-LTQ/Orbitrap MS) was used to screen and confirm 24 banned aromatic amines and their 14 isomers at the same time. The main factors influencing the separation including the column, and the nature of make-up solvent were optimized. Under the optimized experimental conditions, the analytes were reduced to banned aromatic amine with sodium dithionite, extracted by methyl tert-butyl ether and loaded onto a ZORBAX SB-C18 column (150 mm x 2.1 mm, 5 ?m) with a gradient elution of methanol and 0.1% formic acid aqueous solution, and finally detected by LTQ/Orbitrap MS. The screening and quantitative analysis were carried out by the accurate mass of quasi-molecular ion and the peak in extracted chromatogram with accurate mass. The correlation coefficients were higher than 0.99 and the limits of detection were in the range of 0.5-5 ?g/kg. The method could screen and confirm the 24 banned aromatic amines and their 14 isomers at the same time. The results were 1.56 mg/kg of 4-chloroaniline, 0.34 mg/kg of o-toluidine, and 0.81 mg/kg of 2,6-toluylenediamine with the relative standard deviations ranging from 0.27% to 1.32% in actual samples. The results indicate that the developed method is simple, efficient and precise, and can be a reliable technique for the separation of the 24 banned aromatic amines and their 14 isomers in textile samples. PMID:25752096

  18. Rapid screening and confirmation of drugs and toxic compounds in biological specimens using liquid chromatography/ion trap tandem mass spectrometry and automated library search.

    PubMed

    Liu, Hsiu-Chuan; Liu, Ray H; Lin, Dong-Liang; Ho, Hsiu-O

    2010-01-01

    Recent advances in liquid chromatography/tandem mass spectrometry (LC/MS/MS) technology have provided an opportunity for the development of more specific approaches to achieve the 'screen' and 'confirmation' goals in a single analytical step. For this purpose, this study adapts the electrospray ionization ion trap LC/MS/MS instrumentation (LC/ESI-MS/MS) for the screening and confirmation of over 800 drugs and toxic compounds in biological specimens. Liquid-liquid and solid-phase extraction protocols were coupled to LC/ESI-MS/MS using a 1.8-microm particle size analytical column operated at 50 degrees C. Gradient elution of the analytes was conducted using a solvent system composed of methanol and water containing 0.1% formic acid. Positive-ion ESI-MS/MS spectra and retention times for each of the 800 drugs and toxic compounds were first established using 1-10 microg/mL standard solutions. This spectra and retention time information was then transferred to the library and searched by the identification algorithm for the confirmation of compounds found in test specimens - based on retention time matches and scores of fit, reverse fit, and purity resulting from the searching process. The established method was found highly effective when applied to the analyses of postmortem specimens (blood, urine, and hair) and external proficiency test samples provided by the College of American Pathology (CAP). The development of this approach has significantly improved the efficiency of our routine laboratory operation that was based on a two-step (immunoassay and GC/MS) approach in the past. PMID:19957291

  19. Simultaneous determination of diclofenac, its human metabolites and microbial nitration/nitrosation transformation products in wastewaters by liquid chromatography/quadrupole-linear ion trap mass spectrometry.

    PubMed

    Osorio, Victoria; Imbert-Bouchard, Marta; Zonja, Bozo; Abad, José-Luis; Pérez, Sandra; Barceló, Damià

    2014-06-20

    An analytical method was developed and validated for the first determination of five major human metabolites of the non-steroidal anti-inflammatory drug diclofenac as well as two microbial transformation products in wastewater. The method was based on the extraction of diclofenac and the chemically synthetized compounds by solid-phase extraction (SPE), using a hydrophilic-lipophilic balanced polymer followed by liquid chromatography (LC) coupled to hybrid quadrupole-linear ion trap mass spectrometry (QqLIT-MS). Quantitation was performed by the internal standard approach, to correct for matrix effects. The accuracy of the method was generally higher than 40% for raw and treated wastewater with a precision below 12%. In wastewater influent and effluent samples the detection limits for the majority of target compounds were 0.3-2.5ngL(-1) and 0.1-3.1ngL(-1), respectively. The method was applied to the analysis of influent and effluent wastewater samples from urban wastewater treatment plants. Moreover, to obtain an extra tool for confirmation and identification of the studied diclofenac-derived compounds, Information-Dependent Acquisition (IDA) experiments were performed, with selected reaction monitoring (SRM) as the survey scan and an enhanced product ion (EPI) scan as the dependent scan. Diclofenac and its major human metabolite, 4'-hydroxydiclofenac were detected in all samples at concentrations of 331-1150ngL(-1) and 585-6000ngL(-1), respectively. Neither microbial transformation product of diclofenac was detected in any of the influent samples analyzed, but in effluents, their concentrations ranged from 4 to 105ngL(-1). PMID:24835592

  20. Ion Torrent-based transcriptional assessment of a Corynebacterium pseudotuberculosis equi strain reveals denaturing high-performance liquid chromatography a promising rRNA depletion method

    PubMed Central

    Castro, Thiago L P; Seyffert, Nubia; Ramos, Rommel T J; Barbosa, Silvanira; Carvalho, Rodrigo D O; Pinto, Anne Cybelle; Carneiro, Adriana Ribeiro; Silva, Wanderson Marques; Pacheco, Luis G C; Downson, Christopher; Schneider, Maria P C; Miyoshi, Anderson; Azevedo, Vasco; Silva, Artur

    2013-01-01

    Corynebacterium pseudotuberculosis equi is a Gram-positive pathogenic bacterium which affects a variety of hosts. Besides the great economic losses it causes to horse-breeders, this organism is also known to be an important infectious agent to cattle and buffaloes. As an outcome of the efforts in characterizing the molecular basis of its virulence, several complete genome sequences were made available in recent years, enabling the large-scale assessment of genes throughout distinct isolates. Meanwhile, the RNA-seq stood out as the technology of choice for comprehensive transcriptome studies, which may bring valuable information regarding active genomic regions, despite of the still impeditive associated costs. In an attempt to increase the use of generated reads per instrument run, by effectively eliminating unwanted rRNAs from total RNA samples without relying on any commercially available kits, we applied denaturing high-performance liquid chromatography (DHPLC) as an alternative method to assess the transcriptional profile of C.?pseudotuberculosis. We have found that the DHPLC depletion method, allied to Ion Torrent sequencing, allows mapping of transcripts in a comprehensive way and identifying novel transcripts when a de novo approach is used. These data encourage us to use DHPLC in future transcriptional evaluations in C.?pseudotuberculosis. PMID:23316806

  1. Simultaneous detection of perchlorate and bromate using rapid high-performance ion exchange chromatography-tandem mass spectrometry and perchlorate removal in drinking water.

    PubMed

    West, Danielle M; Mu, Ruipu; Gamagedara, Sanjeewa; Ma, Yinfa; Adams, Craig; Eichholz, Todd; Burken, Joel G; Shi, Honglan

    2015-06-01

    Perchlorate and bromate occurrence in drinking water causes health concerns due to their effects on thyroid function and carcinogenicity, respectively. The purpose of this study was threefold: (1) to advance a sensitive method for simultaneous rapid detection of perchlorate and bromate in drinking water system, (2) to systematically study the occurrence of these two contaminants in Missouri drinking water treatment systems, and (3) to examine effective sorbents for minimizing perchlorate in drinking water. A rapid high-performance ion exchange chromatography-tandem mass spectrometry (HPIC-MS/MS) method was advanced for simultaneous detection of perchlorate and bromate in drinking water. The HPIC-MS/MS method was rapid, required no preconcentration of the water samples, and had detection limits for perchlorate and bromate of 0.04 and 0.01 ?g/L, respectively. The method was applied to determine perchlorate and bromate concentrations in total of 23 selected Missouri drinking water treatment systems during differing seasons. The water systems selected include different source waters: groundwater, lake water, river water, and groundwater influenced by surface water. The concentrations of perchlorate and bromate were lower than or near to method detection limits in most of the drinking water samples monitored. The removal of perchlorate by various adsorbents was studied. A cationic organoclay (TC-99) exhibited effective removal of perchlorate from drinking water matrices. PMID:25561263

  2. Studies on the metabolism of mitragynine, the main alkaloid of the herbal drug Kratom, in rat and human urine using liquid chromatography-linear ion trap mass spectrometry.

    PubMed

    Philipp, Anika A; Wissenbach, Dirk K; Zoerntlein, Siegfried W; Klein, Oliver N; Kanogsunthornrat, Jidapha; Maurer, Hans H

    2009-08-01

    Mitragynine (MG) is an indole alkaloid of the Thai medicinal plant Mitragyna speciosa (Kratom in Thai) and reported to have opioid agonistic properties. Because of its stimulant and euphoric effects, Kratom is used as a herbal drug of abuse. The aim of the presented study is to identify the phase I and II metabolites of MG in rat and human urine after solid-phase extraction (SPE) using liquid chromatography-linear ion trap mass spectrometry providing detailed structure information in the MSn mode particularly with high resolution. The seven identified phase I metabolites indicated that MG was metabolized by hydrolysis of the methylester in position 16, O-demethylation of the 9-methoxy group and of the 17-methoxy group, followed, via the intermediate aldehydes, by oxidation to carboxylic acids or reduction to alcohols and combinations of some steps. In rats, four metabolites were additionally conjugated to glucuronides and one to sulfate, but in humans, three metabolites to glucuronides and three to sulfates. PMID:19536806

  3. Soluble arsenic and selenium species in fly ash/organic waste-amended soils using ion chromatography-inductively coupled plasma mass spectrometry

    SciTech Connect

    Jackson, B.P.; Miller, W.P. [Univ. of Georgia, Athens, GA (United States). Dept. of Crop and Soil Sciences] [Univ. of Georgia, Athens, GA (United States). Dept. of Crop and Soil Sciences

    1999-01-15

    Mixing coal fly ash with an organic waste increases macronutrient content and may make land application of fly ash a viable disposal alternative. However, trace element chemistry of these mixed waste products warrants investigation. Speciation of As and Se in soil solutions of fly ash-, poultry litter- and sewage sludge-amended soils was determined over a 10-day period by ion chromatography coupled to inductively coupled plasma mass spectrometry (IC-ICP-MS). Detection limits were 0.031, 0.028, 0.051, 0.161, 0.497, and 0.660 {micro}g L{sup {minus}1} for dimethylarsinate (DMA), As(III), monomethylarsonate (MMA), As(V), Se(IV), and Se(VI), respectively. Arsenic was highly water-soluble from poultry litter and appeared to be predominantly As(V). Arsenic(V) was the predominant species in soil amended with two fly ashes. Application of fly ash/poultry litter mixtures increased As solubility and led to the prevalence of DMA as the major As species. DMA concentrations of these soil solutions decreased rapidly over the sampling period relative to As(V), suggesting that DMA readily underwent mineralization in the soil solution. Se(VI) was the predominant soluble Se species in all treatments indicating rapid oxidation of Se(IV) initially solubilized from the fly ashes.

  4. Characterization of 2-methylglyceric acid oligomers in secondary organic aerosol formed from the photooxidation of isoprene using trimethylsilylation and gas chromatography/ion trap mass spectrometry.

    PubMed

    Szmigielski, Rafal; Surratt, Jason D; Vermeylen, Reinhilde; Szmigielska, Katarzyna; Kroll, Jesse H; Ng, Nga L; Murphy, Shane M; Sorooshian, Armin; Seinfeld, John H; Claeys, Magda

    2007-01-01

    In the present work, we have characterized in detail the chemical structures of secondary organic aerosol (SOA) components that were generated in a smog chamber and result from the photooxidation of isoprene under high-NO(x) conditions typical for a polluted atmosphere. Isoprene high-NO(x) SOA contains 2-methylglyceric acid (2-MG) and oligoester derivatives thereof. Trimethylsilylation, in combination with capillary gas chromatography (GC)/ion trap mass spectrometry (MS) and detailed interpretation of the MS data, allowed structural characterization the polar oxygenated compounds present in isoprene SOA up to 2-MG trimers. GC separation was achieved between 2-MG linear and branched dimers or trimers, as well as between the 2-MG linear dimer and isomeric mono-acetate derivatives thereof. The electron ionization (EI) spectra of the trimethylsilyl derivatives contain a wealth of structural information, including information about the molecular weight (MW), oligoester linkages, terminal carboxylic and hydroxymethyl groups, and esterification sites. Only part of this information can be achieved with a soft ionization technique such as electrospray (ESI) in combination with collision-induced dissociation (CID). The methane chemical ionization (CI) data were used to obtain supporting MW information. Interesting EI spectral differences were observed between the trimethylsilyl derivatives of 2-MG linear and branched dimers or trimers and between 2-MG linear dimer mono-acetate isomers. PMID:17154243

  5. The effect of co-occurring polychlorinated biphenyls on quantitation of toxaphene in fish tissue samples by gas chromatography negative ion mass spectrometry.

    PubMed

    Lao, Wenjian; Tsukada, David; Maruya, Keith A

    2012-12-28

    Determinative methods based on gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS) provide improved sensitivity and specificity for toxaphene in environmental samples, but are subject to misidentification due to oxygen reaction in the presence of polychlorinated biphenyls (PCBs). The goal of this study was to quantify the impact of co-occurring PCBs in fish tissue samples when utilizing single quadrupole instruments to implement this method. Mixtures of PCB congeners and technical toxaphene, and extracts of fish tissue with varying concentrations of PCBs were analyzed for individual congener and total toxaphene concentrations by GC-NCI/MS. The contribution of co-injected PCB 204 ranged from 23% to 88% of the total peak area for the Cl-9 toxaphene homolog quantitation ion, a contribution that increased as the ratio of technical toxaphene to PCB 204 decreased. PCB interferences in fish tissue extracts, including a standard reference material, were subtracted using a three-step procedure featuring spectral analysis of isotopic patterns for target peaks. Total toxaphene concentrations without PCB subtraction in three fish tissue samples with low, intermediate and high co-occurring PCBs were overestimated by 33, 55 and 745%, respectively, underscoring the need for practical strategies to account for PCB interferences in GC-NCI/MS based protocols. In contrast, no appreciable interference or resulting positive bias in concentrations was observed for quantitation of eight common toxaphene residue congeners. PMID:23159199

  6. Study of the enantioselective elimination of four toxaphene congeners in rat after intravenous administration by high resolution gas chromatography negative ion mass spectrometry.

    PubMed

    Skopp, S; Oehme, M; Drenth, H

    2002-02-01

    This study was performed to investigate the possible enantioselective metabolism of the four chlorinated bornanes: #26, #32, #50 and #62 (according to the Parlar nomenclature) by rats. Rats were exposed to a mixture of these toxaphenes by a single intravenous injection. Enantiomer ratios (ER) as well as the enantiomer fractions (EF) were determined in brain, adipose tissue and liver samples at six time intervals by high resolution gas chromatography (HRGC) coupled to negative ion chemical ionization (NICI) mass spectrometry (MS). Capillaries coated with heptakis-(2,3,6-O-tert-butyldimethylsilyl)-beta-cyclodextrin (TBDMS-CD) or octakis-(2,3,6-tri-O-ethyl)-gamma-cyclodextrin (TEG-CD) were used for the enantioselective separations. Significant time-dependent changes of ER and EF were found in all the three tissues for #26, #50 and #62. Greatest deviations from racemic composition were found in the liver, which is known to be the major metabolizing organ for toxaphenes. #32 was metabolized the fastest, but showed no changes in ER. Brief information is also included about the possible reasons for the different behaviors of the four congeners in the studied tissues. PMID:11999771

  7. Physicochemical properties of silica gel coated with a thin layer of polyaniline (PANI) and its application in non-suppressed ion chromatography.

    PubMed

    Sowa, Ireneusz; Kocjan, Ryszard; Wójciak-Kosior, Magdalena; Swieboda, Ryszard; Zajdel, Dominika; Hajnos, Mieczys?aw

    2013-10-15

    Physicochemical properties of a new sorbent and its potential application in non-suppressed ion chromatography (IC) have been investigated. The sorbent was obtained in a process of covering silica gel particles with a film of polyaniline (PANI). The properties of silica modified with polyaniline such as particle size, porosity, average quantity of polyaniline covering carrier and density of sorbent were determined. In our study the following methods were used: microscopic analysis, laser diffraction technique, combustion analysis, mercury porosimetry and helium pycnometry. Column with the newly obtained packing was used for the separation of inorganic anions. Optimized chromatographic system was successfully employed for analysis of iodide and bromide in selected pharmaceutical products (Bochnia salt and Iwonicz salt) applied in chronic respiratory disease. Analysis was carried out using 0.1M solution of HCl in mixture of methanol/water (50:50v/v) as a mobile phase; the flow rate was 0.3 mL min(-1), temperature was 24°C and ?=210 nm. Validation parameters such as correlation coefficient, RSD values, recovery, detection and quantification limits were found to be satisfactory. PMID:24054617

  8. Quantitative determination of selected compounds in a Kentucky 1R4F reference cigarette smoke by multidimensional gas chromatography and selected ion monitoring-mass spectrometry.

    PubMed

    White, E L; Uhrig, M S; Johnson, T J; Gordon, B M; Hicks, R D; Borgerding, M F; Coleman, W M; Elder, J F

    1990-08-01

    Eight compounds from a Kentucky 1R4F reference cigarette smoke condensate have been determined by selected ion monitoring-mass spectrometry (SIM-MS) to confirm the validity of multidimensional gas chromatography (MDGC) as a quantitative tool in complex mixture analyses. Four electrostatically precipitated smoke condensate samples of 100 cigarettes each are dissolved individually in 25 mL of 2-propanol. The 2-propanol contains two methyl esters (C8 and C14) and seven deuterium-labeled compounds used as internal standards (IS). Analysis of the compounds of interest, pyridine; acetamide; acrylamide; phenol; o-, m-, and p-cresol; and quinoline, is accomplished by using two heartcuts. Heartcut times of the MDGC analysis are selected such that at least one IS is transferred with each group of compounds being analyzed. This study shows that the MDGC technique previously developed and described can be used for quantitative analyses. A comparison is made between the two types of internal standards. The results obtained for both types of internal standards agree within 20% of each other, on the average, with higher standard deviations for approximately 60% of the compounds where methyl esters are used as internal standards. PMID:2229269

  9. In vitro metabolism study of Strychnos alkaloids using high-performance liquid chromatography combined with hybrid ion trap/time-of-flight mass spectrometry.

    PubMed

    Tian, Ji-Xin; Peng, Can; Xu, Lei; Tian, Yuan; Zhang, Zun-Jian

    2013-06-01

    In this report, the in vitro metabolism of Strychnos alkaloids was investigated using liquid chromatography/high-resolution mass spectrometry for the first time. Strychnine and brucine were selected as model compounds to determine the universal biotransformations of the Strychnos alkaloids in rat liver microsomes. The incubation mixtures were separated by a bidentate-C18 column, and then analyzed by on-line ion trap/time-of-flight mass spectrometry. With the assistance of mass defect filtering technique, full-scan accurate mass datasets were processed for the discovery of the related metabolites. The structural elucidations of these metabolites were achieved by comparing the changes in accurate molecular masses, calculating chemical component using Formula Predictor software and defining sites of biotransformation based upon accurate MS(n) spectral information. As a result, 31 metabolites were identified, of which 26 metabolites were reported for the first time. These biotransformations included hydroxylation, N-oxidation, epoxidation, methylation, dehydrogenation, de-methoxylation, O-demethylation, as well as hydrolysis reactions. PMID:23348426

  10. Polar organic chemical integrative sampling and liquid chromatography- electrospray/ion-trap mass spectrometry for assessing selected prescription and illicit drugs in treated sewage effluents

    USGS Publications Warehouse

    Jones-Lepp, T. L.; Alvarez, D.A.; Petty, J.D.; Huckins, J.N.

    2004-01-01

    The purpose of the research presented in this paper was twofold: (1) to demonstrate the coupling of two state-of-the-art techniques: a time-weighted polar organic chemical integrative sampler (POCIS) and microliquid chromatography-electrospray/ion-trap mass spectrometry and (2) to assess the ability of these methodologies to detect six drugs (azithromycin, fluoxetine, omeprazole, levothyroxine, methamphetamine, methylenedioxymethamphetamine [MDMA]) in a real-world environment, e.g., waste water effluent. In the effluent from three wastewater treatment plants (WWTPs), azithromycin was detected at concentrations ranging from 15 to 66 ng/L, which is equivalent to a total annual release of 1 to 4 kg into receiving waters. Detected and confirmed in the effluent from two WWTPs were two illicit drugs, methamphetamine and MDMA, at 2 and 0.5 ng/L, respectively. Although the ecotoxicologic significance of drugs in environmental matrices, particularly water, has not been closely examined, it can only be surmised that these substances have the potential to adversely affect biota that are continuously exposed to them even at very low levels. The potential for chronic effects on human health is also unknown but of increasing concern because of the multi-use character of water, particularly in densely populated, arid areas.

  11. Rapid determination of para-phenylenediamine by gas chromatography-mass spectrometry with selected ion monitoring in henna-containing cosmetic products.

    PubMed

    Wang, Perry G; Krynitsky, Alexander J

    2011-06-15

    A rapid method for the determination of para-phenylenediamine (PPD) in cosmetic products, such as henna tattoos has been developed and evaluated. This analytical procedure involved extracting a 10mg test portion of cosmetic product in 10 mL of ethyl acetate, followed by determination by gas chromatography-mass spectrometry in the selected ion monitoring mode (GC/MS-SIM). 1,4-Phenylenediamine-2,3,5,6-d(4) was selected as an internal standard that was added at the beginning of the extraction procedure and used to correct for recovery and matrix effects. The linearity ranged from 1.0 to 1275 ?g/mL with a coefficient of determination (r(2)) greater than 0.999. LOQ and LOD were 1.0 and 0.10 ?g/mL, respectively. The recovery in a tattoo product containing PPD was 94% and that for a tattoo product containing no PPD reached 105%. Extraction efficiency of 98% was obtained. This method has been successfully applied to henna temporary tattoo and other henna-related cosmetic products for the determination and quantitation of PPD. PMID:21606006

  12. Determination of actinides in environmental and biological samples using high-performance chelation ion chromatography coupled to sector-field inductively coupled plasma mass spectrometry.

    PubMed

    Truscott, J B; Jones, P; Fairman, B E; Evans, E H

    2001-08-31

    High-performance chelation ion chromatography, using a neutral polystyrene substrate dynamically loaded with 0.1 mM dipicolinic acid, coupled with sector-field inductively coupled plasma mass spectrometry has been successfully used for the separation of the actinides thorium, uranium, americium, neptunium and plutonium. Using this column it was possible to separate the various actinides from each other and from a complex sample matrix. In particular, it was possible to separate plutonium and uranium to facilitate the detection of the former free of spectral interference. The column also exhibited some selectivity for different oxidation states of Np, Pu and U. Two oxidation states each for plutonium and neptunium were found, tentatively identified as Np(V) and Pu(III) eluting at the solvent front, and Np(IV) and Pu(IV) eluting much later. Detection limits were 12, 8, and 4 fg for 237Np, 239Pu, and 241Am, respectively, for a 0.5 ml injection. The system was successfully used for the determination of 239Pu in NIST 4251 Human Lung and 4353 Rocky Flats Soil, with results of 570+/-29 and 2939+/-226 fg g(-1), respectively, compared with a certified range of 227-951 fg g(-1) for the former and a value of 3307+/-248 fg g(-1) for the latter. PMID:11589474

  13. Analytical protocol for the sensitive determination of mannitol, sorbitol and glucose containing powders in pharmaceutical workplaces by ion chromatography using a pulsed amperometric detector.

    PubMed

    Butler, Owen; Forder, James; Saunders, John

    2015-03-15

    Workers in the pharmaceutical industry can potentially be exposed to airborne dusts and powders that can contain potent active pharmaceutical ingredients (API). Occupational hygienists and health and safety professionals need to assess and ultimately minimise such inhalation and dermal exposure risks. Containment of dusts at source is the first line of defence but the performance of such technologies needs to be verified, for which purpose the good practice guide: assessing the particulate containment performance of pharmaceutical equipment, produced by the International Society for Pharmaceutical Engineering (ISPE), is a widely used reference document. This guide recommends the use of surrogate powders that can be used to challenge the performance of such containment systems. Materials such as lactose and mannitol are recommended as their physical properties (adhesion, compactability, dustiness, flow characteristics and particle sizes) mimic those of API-containing materials typically handled. Furthermore they are safe materials to use, are available in high purity and can be procured at a reasonable cost. The aim of this work was to develop and validate a sensitive ion-chromatography based analytical procedure for the determination of surrogate powders collected on filter samples so as to meet analytical requirements set out in this ISPE guide. PMID:25459267

  14. Quantitative determination of isoquinoline alkaloids and chlorogenic acid in Berberis species using ultra high performance liquid chromatography with hybrid triple quadrupole linear ion trap mass spectrometry.

    PubMed

    Singh, Awantika; Bajpai, Vikas; Kumar, Sunil; Arya, Kamal Ram; Sharma, Kulwant Rai; Kumar, Brijesh

    2015-06-01

    Berberis species are well known and used extensively as medicinal plants in traditional medicine. They have many medicinal values attributable to the presence of alkaloids having different pharmacological activities. In this study, a method was developed and validated as per international conference on harmonization guidelines using ultra high performance liquid chromatography with hybrid triple quadrupole-linear ion trap mass spectrometry operated in the multiple reaction monitoring mode for nine bioactive compounds, including protoberberine alkaloids, aporphine alkaloids and chlorogenic acid. This method was applied in different plant parts of eight Berberis species to determine variations in content of nine bioactive compounds. The separation was achieved on an ACQUITY UPLC CSH™ C18 column using a gradient mobile phase at flow rate 0.3 mL/min. Calibration curves for all the nine analytes provided optimum linear detector response (with R(2) ?0.9989) over the concentration range of 0.5-1000 ng/mL. The precision and accuracy were within RSDs ?2.4 and ?2.3%, respectively. The results indicated significant variation in the total contents of the nine compounds in Berberis species. PMID:25847792

  15. Concentration and separation of trace metal ions by reversed-phase adsorption chromatography. [bis(2-hydroxyethyl)dithiocarbamate (HEDC), 1,3-dimethyl-4-acetyl-2-pyrazolin-5-one (DMAP)

    Microsoft Academic Search

    1986-01-01

    The concentration and separation of trace metal ions chelated with either bis(2-hydroxyethyl)dithiocarbamate (HEDC) or 1,3-dimethyl-4-acetyl-2-pyrazolin-5-one (DMAP) by reversed-phase adsorption chromatography has been studied. The concentration of metals of the hydrogen sulfide group from very dilute solution by chelation with HEDC and subsequent adsorption on a small column of Amberlite XAD-4 resin is described. Selectivity is achieved by pH adjustment or

  16. Separation of isomeric octadecenoic fatty acids in partially hydrogenated vegetable oils as p-methoxyphenacyl esters using a single-column silver ion high-performance liquid chromatography (Ag-HPLC)

    Microsoft Academic Search

    Svetlana M Momchilova; Boryana M Nikolova-Damyanova

    2010-01-01

    A protocol for separation of positionally isomeric trans- and cis-octadecenoic fatty acids as their p-methoxyphenacyl esters, using a single column silver ion high-performance liquid chromatography (Ag-HPLC) with UV detection, is described. The procedure involves hydrolysis of oil to free fatty acids, derivatization to p-methoxyphenacyl esters, purification and separation by Ag-HPLC. The procedure is robust and relatively rapid. In total, it

  17. [Simultaneous determination of nine beta-blockers in porcine tissues by ultra-fast liquid chromatography coupled with quadrupole/linear ion trap mass spectrometry].

    PubMed

    Zhang, Hongwei; Xu, Hui; Gao, Jianguo; Liang, Chengzhu; Xu, Biao; Geng, Juan; Wang, Fengmei; Zhang, Xiaomei; Cheng, Gang

    2014-06-01

    A highly sensitive method using ultra-fast liquid chromatography coupled with quadrupole/linear ion trap mass spectrometry (UFLC-Q/Trap MS) was developed to simultaneously screen and confirm nine beta-blockers (BBs) in porcine tissues (porcine muscle, liver and kidney). The method was used for trace determination of atenolol, pindolol, acebutolol, metoprolol, carazolol, labetalol, bisoprolol, propranolol and penbutolol. The homogenized tissues were hydrolyzed by beta-glucuronidase/aryl sulfatase and extracted with acetonitrile, followed by continuous purification procedures of disperse solid phase extraction (d-SPE) with diatomaceous earth and BondElut cartridge. The ultra-fast chromatographic separation was conducted on a Kinetex C18-XB column (150 mm x 2.1 mm, 2.6 microm) using 0.1% (v/v) formic acid aqueous solution and methanol as mobile phases in gradient elution. The optimized ion transitions were mployed in the mixed-mode of scheduled multiple reaction monitoring (sMRM) -information dependent acquisition (IDA)-enhanced product ion (EPI) scan. Qualification analysis was performed through spectra-matching with on-line lab-built MS/MS library. For quantification stable isotope-labelled analogues of the analytes were used as internal standards. As a result, in porcine liver, kidney and muscle, the nine BBs showed good linearity with all the correlation coefficients (r) more than 0.995 in the range of 0.1-20 microg/L. The limits of quantification (LOQ, S/N > or = 10) were 0.5 kg/kg for all the analytes. The developed method gave average recoveries of 87.5%-111.8% spiked at 0.5, 1.0 and 5.0 microg/kg with the relative standard deviations of 4.0%-12. 5%. The proposed method can be used to screen and confirm the nine BBs in a single run, which makes it effective in surveillance and detection of the BBs residues in porcine tissues. PMID:25269253

  18. Speciation of selenium in plant water extracts by ion exchange chromatography-hydride generation atomic absorption spectrometry.

    PubMed

    Zhang, Y; Frankenberger, W T

    2001-03-26

    Determination of selenium (Se) speciation in plants is important in studying the bioavailability and toxicity of Se in Se-contaminated soil/sediment. In this study, we used an anion exchange resin (Dowex 1-10X) to separate Se into non-amino acid organic Se, Se-amino acids, selenite (Se [IV]) and selenate (Se [VI]) in a plant (Stanleya pinnata) extract. The hydride generation atomic absorption spectrometry (HGAAS) was used to determine concentrations of these Se compounds in plant extracts. Results showed that Se compounds can be quantitatively separated by the resin column. Recovery of five spiked standard Se compounds (trimethylselenonium ion (TMSe+), dimethylselenoxide (DMSeO), selenomethionine (Semet), Se [IV] and Se [VII]) in the plant extract ranged from 92.9 to 103%. Water extractable Se accounted for 60.4-72.6% of the total Se in the plant. Among the soluble Se compounds in the plant extract, Se-amino acids were 73-85.5%, Se [VI] ranged from 7.5 to 19.5% and non-amino acid organic Se was less than 7%. Se [IV] in most samples was below the detection limit (1 microg/g). This study showed that considerable amounts of the accumulated Se [VI] in the plant was metabolized to Se-amino acids during growth of the plant. PMID:11305342

  19. Ion chromatography as a novel method to quantify the solubility of pyridinium ionic liquids in organic solvents.

    PubMed

    Onink, Ferdy; Meindersma, Wytze; Burghoff, Bernhard; Weggemans, Wilko; Aerts, Guus; de Haan, André

    2015-01-01

    A validated ion chromatographic method was developed and applied for the determination of the maximum solubility of pyridinium ionic liquids in several aromatic solvents. Elution was performed on a Metrosep C3-150 prototype column at 40°C with acetonitrile-water at a flow rate of 1.0 mL min(-1). Mixtures of pyridinium ionic liquids and aromatic solvents were diluted with acetonitrile and acetone on a 1:1:2 weight base before the analysis. The chromatographic time only took 20 min. The standard curves for both pyridinium ionic liquids ([4-mebupy]BF4 and [3-mebupy]N(CN)2) were linear (r(2) = 0.9980-0.9998) in all aromatic solvents (toluene, benzene, ethylbenzene and o-xylene) in the concentration range of 5.37-241 mg kg(-1). The intraday relative standard deviations (n = 3) for peak areas were 0.60-2.9%. Accuracy in the measurement of samples ranged from 98.5 to 105%. The limit of detection for both pyridinium ionic liquids in all solvents varied between 0.73 and 2.6 mg kg(-1). This assay has been successfully applied in the determination of the maximum solubilities of both pyridinium ionic liquids in several aromatic solvents. This method demonstrated that with increasing aromatic character and/or temperature the solubilities of both investigated pyridinium ILs in the aromatic solvents increase. This is primary caused by the nature of the anion. PMID:24552669

  20. Matrix Elimination Ion Chromatography Method for the Determination of Trace Levels of Anionic Impurities in High Purity Cesium Iodide

    PubMed Central

    Ayushi; Kumar, Sangita D.; Reddy, A.V.R.

    2012-01-01

    In the present study an ion chromatographic method based on matrix elimination has been developed for the determination of anionic impurities in high purity cesium iodide crystals. The presence of impurities has a detrimental effect on the characteristics of detectors based on cesium iodide crystals. In particular, oxygen-containing anions inhibit the resolving power of scintillators and decrease the optical absorption. The quantitative determination of anions (fluoride, chloride, bromide, nitrate, phosphate, and sulphate) simultaneously in the high-purity cesium iodide crystals has not been carried out before. The large concentration of iodide poses a challenge in the determination of anions (especially phosphate and sulphate); hence, matrix elimination is accomplished by adopting a sample pretreatment technique. The method is validated for linearity, accuracy, and precision. The limit of detection for different anions is in the range of 0.3–3 µg/g, and the relative standard deviation is in the range of 4–6% for the overall method. PMID:22291061

  1. Determination of trace amounts of nitrogen in uranium based samples by ion chromatography (IC) without Kjeldahl distillation.

    PubMed

    Verma, Poonam; Rastogi, Ramakant K; Ramakumar, Karanam L

    2007-07-23

    A simple, sensitive and fast ion chromatographic (IC) method with suppressed conductivity detection is described for the determination of traces of nitrogen in uranium based fuel materials. Initially a method was developed to determine nitrogen as NH4(+) using cation exchange column after matrix separation by Kjeldahl distillation. The method was then improved by eliminating this distillation. Matrix separation after sample dissolution was done by hydrolyzing and filtering off the polyvalent cations. This had helped in reducing both the sample size and analysis time. Optimization of dissolution conditions for various kinds of uranium based samples was done to keep acid content minimum; a prerequisite chromatographic condition. The calibration plot for nitrogen was linear in the concentration range of 0.02-1 mg L(-1) with regression coefficient of 0.9999. The relative standard deviation (R.S.D.) obtained in this method (100 microL injected) was 3% and 2% in 9 replicates at nitrogen level of 28 and 55 ng g(-1), respectively. Detection limit based on S/N=3 (100 microL injected) as well as three times of variation in blank value was 4 ng g(-1). The developed method was authenticated by comparison with certified uranium-alloy standard as well as with independent indophenol photometry method. The developed method was applied to uranium-alloy, uranium-metal, sintered UO2 pellets and sintered UO2 microspheres samples. PMID:17631107

  2. 37 CFR 404.7 - Exclusive, co-exclusive and partially exclusive licenses.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...2011-07-01 2011-07-01 false Exclusive, co-exclusive and partially exclusive licenses...OWNED INVENTIONS § 404.7 Exclusive, co-exclusive and partially exclusive licenses. (a)(1) Exclusive, co-exclusive or partially exclusive...

  3. Affinity Chromatography

    NSDL National Science Digital Library

    Using exposition, graphics, and commercial videos, this module teaches the theory and application of affinity chromatography in the characterization of proteins, nucleic acids, and other biochemical/biomedical systems. Problems and application examples support the tutorial material.

  4. Direct comparison between ion-exchange chromatography and aqueous two-phase processes for the partial purification of penicillin acylase produced by E. coli

    Microsoft Academic Search

    Oscar Aguilar; Verónica Albiter; Leobardo Serrano-Carreón; Marco Rito-Palomares

    2006-01-01

    A direct comparison of a chromatography and an aqueous two-phase system (ATPS) processes for the partial purification of penicillin acylase (PA) produced by a recombinant strain of E. coli, was performed. An established chromatography process for the recovery of PA was selected as a model system and characterised for comparison with a developed ATPS prototype process. PEG-phosphate systems were selected

  5. Structural characterization of synthetic polymers and copolymers using multidimensional mass spectrometry interfaced with thermal degradation, liquid chromatography and/or ion mobility separation

    NASA Astrophysics Data System (ADS)

    Alawani, Nadrah

    This dissertation focuses on coupling mass spectrometry (MS) and tandem mass spectrometry (MS/MS) to thermal degradation, liquid chromatography (LC) and/or ion mobility (IM) spectrometry for the characterization of complex mixtures. In chapter II, an introduction of the history and the principles of MS and LC are discussed. Chapter III illustrates the materials and instrumentation used to complete this dissertation. Polyethers have been characterized utilizing MS/MS, as presented in Chapter IV and Chapter VI. Diblock copolymers of polyethylene oxide and polycaprolactone, PEO-b-PCL, have been characterized by matrix-assisted laser desorption/ionization quadrupole/time-of-flight mass spectrometry (MALDI-Q/ToF) and LC-MS/MS (Chapter V). Thermoplastic elastomers have been characterized by thermal degradation using an atmospheric solids analysis probe (ASAP) and ion mobility mass spectrometry (IM-MS), as discussed in Chapter VII. Interfacing separation techniques with mass spectrometry permitted the detection of species present with low concentration in complex materials and improved the sensitivity of MS. In chapter IV, the fragmentation mechanisms in MS/MS experiments of cyclic and linear poly(ethylene oxide) macroinitiators are discussed. This study aimed at determining the influence of end groups on the fragmentation pathways. In the study reported in Chapter V, ultra high performance liquid chromatography (UHPLC) was interfaced with MS and MS/MS to achieve the separation and in-depth characterization and separation of amphiphilic diblock copolymers (PEO- b-PCL) in which the architecture of the PEO block is linear or cyclic. Applying UPLC-MS and UPLC-MS/MS provides fast accurate information about the number and type of the blocks in the copolymers. Chapter VI reports MS/MS and IM-MS analyses which were performed to elucidate the influence of molecular size and collision energy on the fragmentation pathways of polyethers subjected to collisionally activated dissociation. Survival yields and collision cross-sections were derived for several oligomers of polyethers by MS/MS and IM-MS, in order to understand their fragmentation energetics and fully characterize their structures. In Chapter VII, application of ASAP and IM separation were coupled with MS and MS/MS to characterize commercially available thermoplastic elastomers. These compounds are mainly composed of thermoplastic copolymers, but also contain additional chemicals to enhance their properties or to protect them from degradation. Using ASAP-IM-MS enables fast analysis, involving mild degradation at ASAP and subsequent characterization of the desorbates and pyrolyzates by IM-MS and MS/MS. Such multidimensional dispersion considerably simplifies the resulting spectra, permitting the conclusive separation and characterization of the multicomponent materials examined. Chapter VIII summarizes the findings of this dissertation and is followed by appendices.

  6. Targeted Metabolomic Analysis of Head and Neck Cancer Cells Using High Performance Ion Chromatography Coupled with a Q Exactive HF Mass Spectrometer.

    PubMed

    Hu, Shen; Wang, Junhua; Ji, Eoon Hye; Christison, Terri; Lopez, Linda; Huang, Yingying

    2015-06-16

    In this study, we have demonstrated a targeted metabolomics method for analysis of cancer cells, based on high-performance ion chromatography (IC) separation, Q Exactive HF MS for high-resolution and accurate-mass (HR/AM) measurement and the use of stable isotope-labeled internal standards for absolute quantitation. Our method offers great technical advantages for metabolite analysis, including exquisite sensitivity, high speed and reproducibility, and wide dynamic range. The high-performance IC provided fast separation of cellular metabolites within 20 min and excellent resolving power for polar molecules including many isobaric metabolites. The IC/Q Exactive HF MS achieved wide dynamic ranges of 5 orders of magnitude for six targeted metabolites, pyruvate, succinic acid, malic acid, citric acid, fumaric acid, and alpha-ketoglutaric acid, with R(2) ? 0.99. Using this platform, metabolites can be simultaneously quantified from low fmol/?L to nmol/?L levels in cellular samples. The high flow rate IC at 380 ?L/min has shown excellent reproducibility for a large set of samples (150 injections), with minimal variations of retention time (SD < ± 0.03 min). In addition, the IC-MS-based approach acquires targeted and global metabolomic data in a same analytical run, and the use of stable isotope-labeled standards facilitates accurate quantitation of targeted metabolites in large-scale metabolomics analysis. This metabolomics approach has been successfully applied to analysis of targeted metabolites in head and neck cancer cells as well as cancer stem-like cells (CSCs), and the findings indicate that the metabolic phenotypes may be distinct between high and low invasive head and neck cancer cells and between CSCs and non-SCCs. PMID:25973679

  7. An introduction to hybrid ion trap/time-of-flight mass spectrometry coupled with liquid chromatography applied to drug metabolism studies.

    PubMed

    Liu, Zhao-Ying

    2012-12-01

    Metabolism studies play an important role at various stages of drug discovery and development. Liquid chromatography combined with mass spectrometry (LC/MS) has become a most powerful and widely used analytical tool for identifying drug metabolites. The suitability of different types of mass spectrometers for metabolite profiling differs widely, and therefore, the data quality and reliability of the results also depend on which instrumentation is used. As one of the latest LC/MS instrumentation designs, hybrid ion trap/time-of-flight MS coupled with LC (LC-IT-TOF-MS) has successfully integrated ease of operation, compatibility with LC flow rates and data-dependent MS(n) with high mass accuracy and mass resolving power. The MS(n) and accurate mass capabilities are routinely utilized to rapidly confirm the identification of expected metabolites or to elucidate the structures of uncommon or unexpected metabolites. These features make the LC-IT-TOF-MS a very powerful analytical tool for metabolite identification. This paper begins with a brief introduction to some basic principles and main properties of a hybrid IT-TOF instrument. Then, a general workflow for metabolite profiling using LC-IT-TOF-MS, starting from sample collection and preparation to final identification of the metabolite structures, is discussed in detail. The data extraction and mining techniques to find and confirm metabolites are discussed and illustrated with some examples. This paper is directed to readers with no prior experience with LC-IT-TOF-MS and will provide a broad understanding of the development and utility of this instrument for drug metabolism studies. PMID:23280752

  8. Pathway Confirmation and Flux Analysis of Central Metabolic Pathways in Desulfovibrio vulgaris Hildenborough using Gas Chromatography-Mass Spectrometry and Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry? †

    PubMed Central

    Tang, Yinjie; Pingitore, Francesco; Mukhopadhyay, Aindrila; Phan, Richard; Hazen, Terry C.; Keasling, Jay D.

    2007-01-01

    Flux distribution in central metabolic pathways of Desulfovibrio vulgaris Hildenborough was examined using 13C tracer experiments. Consistent with the current genome annotation and independent evidence from enzyme activity assays, the isotopomer results from both gas chromatography-mass spectrometry (GC-MS) and Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) indicate the lack of an oxidatively functional tricarboxylic acid (TCA) cycle and an incomplete pentose phosphate pathway. Results from this study suggest that fluxes through both pathways are limited to biosynthesis. The data also indicate that >80% of the lactate was converted to acetate and that the reactions involved are the primary route of energy production [NAD(P)H and ATP production]. Independently of the TCA cycle, direct cleavage of acetyl coenzyme A to CO and 5,10-methyl tetrahydrofuran also leads to production of NADH and ATP. Although the genome annotation implicates a ferredoxin-dependent oxoglutarate synthase, isotopic evidence does not support flux through this reaction in either the oxidative or the reductive mode; therefore, the TCA cycle is incomplete. FT-ICR MS was used to locate the labeled carbon distribution in aspartate and glutamate and confirmed the presence of an atypical enzyme for citrate formation suggested in previous reports [the citrate synthesized by this enzyme is the isotopic antipode of the citrate synthesized by the (S)-citrate synthase]. These findings enable a better understanding of the relation between genome annotation and actual metabolic pathways in D. vulgaris and also demonstrate that FT-ICR MS is a powerful tool for isotopomer analysis, overcoming the problems with both GC-MS and nuclear magnetic resonance spectroscopy. PMID:17114264

  9. Simultaneous determination of bromate, chlorite and haloacetic acids by two-dimensional matrix elimination ion chromatography with coupled conventional and capillary columns.

    PubMed

    Teh, Hui Boon; Li, Sam Fong Yau

    2015-02-27

    A new, highly sensitive and reliable two-dimensional matrix elimination ion chromatography (IC) method was developed for simultaneous detection of bromate, chlorite and five haloacetic acids. This method combined the conventional IC in first dimension with capillary IC in the second dimension coupled with suppressed conductivity detection. The first dimension utilizes a high capacity column to partially resolve matrix from target analytes. By optimizing the cut window, the target analytes were selectively cut and trapped in a trap column through the use of a six-port valve, while the separated matrix were diverted to waste. The trapped target analytes were delivered on to the capillary column for further separation and detection. Temperature programming was used to improve selectivity in second dimension column to obtain complete resolution of the target analytes. Compared to the performance of one-dimensional IC, the two-dimensional approach resulted in a significant increase in sensitivity for all target analytes with limit of detection ranging from 0.30 to 0.64?g/L and provided more reliable analysis due to second column confirmation. Good linearity was obtained for all the target analytes with correlation coefficients >0.998. The proposed method was successfully applied to the determination of oxyhalides and haloacetic acids in various matrices with recoveries ranging from 90 to 116% and RSD less than 6.1%. The method allows direct injection of samples and the use of columns with different selectivity, thus significantly reduces the level of false positive results. The method is fully automated and simple, making it practical for routine monitoring of water quality. The satisfactory results also demonstrated that the two-dimensional matrix elimination method coupled with capillary IC is a promising approach for detection of trace substances in complex matrices. PMID:25650354

  10. Multiresidue analytical method using dispersive solid-phase extraction and gas chromatography/ion trap mass spectrometry to determine pharmaceuticals in whole blood.

    PubMed

    Plössl, Florian; Giera, Martin; Bracher, Franz

    2006-11-24

    A convenient analytical method for the simultaneous determination of more than 40 pharmaceuticals belonging to various therapeutic categories in whole blood has been developed. Exemplarily, the method was fully validated for eight different pharmaceuticals. The procedure entails addition of acetonitrile, magnesium sulfate and sodium chloride to a small amount of blood, then the mixture is shaken intensively and centrifuged for phase separation. An aliquot of the organic layer is cleaned up by dispersive solid-phase extraction employing bulk sorbents as well as magnesium sulfate for the removal of residual water. This method was based on the QuEChERS approach developed for pesticide residue analysis in food. Gas chromatography/ion trap mass spectrometry (GC/MS) with electron (EI) and chemical (CI) ionisation was then used for qualitative and quantitative determination of the pharmaceuticals. The dispersive SPE with PSA (sorbent functionalized with primary and secondary amines) was found more suitable than aminopropyl and a styrene-divinylbenzene sorbent for sample clean-up before drug level determination in whole blood and plasma, as it was found that most of endogenous matrix components were removed and the analytes were isolated from spiked samples with recoveries above 80%. Variation coefficients of the repeatability typically smaller than 10% have been achieved for a wide range of the investigated substances. The used analytical conditions allowed to separate successively a variety of drugs and poisons with the typical limit of detection at <20 ng mL(-1) levels using 1 microL injection of equivalent blood sample in whole blood. The method is simple, rapid, cheap and very effective for therapeutic drug monitoring and forensic chemistry. PMID:17049535

  11. Simultaneous determination of Cr(III) and Cr(VI) in tannery wastewater using low pressure ion chromatography combined with flow injection spectrophotometry

    NASA Astrophysics Data System (ADS)

    Chen, Shujuan; Zhang, Xinshen; Yu, Lingyun; Wang, Li; Li, Hui

    2012-03-01

    Trivalent and hexavalent chromium have been successfully separated and determined using low pressure ion chromatography combined with flow injection spectrophotometric analysis (LPIC-FIA). A column packed with crosslinking starch microspheres was used for on-line separation of Cr(III) from Cr(VI) in a flow-injection system because of its absorptive effect on Cr(III). To determine the concentration of Cr(III) and Cr(VI) in samples, we used 3.0 mmol/L nitric acid to elute adsorbed Cr(III) from the column and then used ceric sulfate-sulfuric acid as oxidant to convert all Cr(III) into Cr(VI). Then, Cr(VI) directly came from the samples and Cr(VI) came from Cr(III) successively formed a amaranthine complex with diphenycarbazide and the complex shows a maximum absorption at 530 nm. Analytical parameters including the concentration of eluent and oxidant solution, oxidizing temperature, length of oxidizing reaction coil, reaction coil and injection coil, interfering effects, etc., were optimized. The limit of detection was 1.25 ?g/L for Cr(VI) and 3.76 ?g/L for Cr(III). The linear relationship between absorption with the concentration of Cr(VI) and Cr(III) was 0.001-1.000 mg/L and 0.030-1.000 mg/L with correlation coefficients of 0.9995 and 0.9994, respectively. The relative standard deviation of Cr(VI) and Cr(III) was 1.21% and 1.66%, respectively (n = 10). Major cations and anions did not show any interference. We validated this method through certified reference materials and through measuring the recovery in tannery wastewater.

  12. Simultaneous determination of Cr(iii) and Cr(vi) using reversed-phased ion-pairing liquid chromatography with dynamic reaction cell inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Wolf, R.E.; Morrison, J.M.; Goldhaber, M.B.

    2007-01-01

    A method for the simultaneous determination of Cr(iii) and Cr(vi) species in waters, soil leachates and synthetic bio-fluids is described. The method uses reversed-phase ion-pairing liquid chromatography to separate the chromium species and a dynamic reaction cell (DRC??) equipped ICP-MS for detection of chromium. Separation of the chromium species is carried out in less than 2 min. Cr(iii) is complexed with ethylenediaminetetraacetic acid (EDTA) prior to separation by mixing samples with the mobile phase containing 2.0 mM tetrabutylammonium hydroxide (TBAOH), 0.5 mM EDTA (dipotassium salt), and 5% (vol/vol) methanol, adjusted to pH 7.6. The interfering 40Ar 12C+ background peak at mass 52 was reduced by over four orders of magnitude to less than 200 cps by using 0.65 mL min-1 ammonia as a reaction gas and an RPq setting on the DRC of 0.75. Method detection limits (MDLs) of 0.09 ??g L-1 for Cr(iii) and 0.06 ??g L-1 for Cr(vi) were obtained based on peak areas at mass 52 for 50 ??L injections of low level spikes. Reproducibility at 2 ??g L-1 was 3% RSD for 5 replicate injections. The tolerance of the method to various levels of common cations and anions found in natural waters and to matrix constituents found in soil leachates and simulated gastric and lung fluids was tested by performing spike recovery calculations for a variety of samples. ?? The Royal Society of Chemistry.

  13. Ions

    MedlinePLUS

    ... Ions with a positive charge are called cations. Ions with a negative charge are called anions. Many normal substances exist in the body as ions. Common examples include sodium, potassium, calcium, chloride, and ...

  14. Determination of naltrexone and 6-beta-naltrexol in plasma by solid-phase extraction and gas chromatography-negative ion chemical ionization-mass spectrometry.

    PubMed

    Huang, W; Moody, D E; Foltz, R L; Walsh, S L

    1997-01-01

    Solid-phase extraction (SPE) and a one-step derivatization are combined with gas chromatography-negative ion chemical ionization-mass spectrometry to simplify a previously reported method for the determination of naltrexone and its metabolite, 6-beta-naltrexol, in human plasma. Deuterated isotopomers of naltrexone and 6-beta-naltrexol are used as internal standards. After SPE, the extracts are derivatized with pentafluoropropionic anhydride at room temperature to form predominantly the bispentafluoropropionyl derivative of naltrexone and the trispentafluoropropionyl derivative of 6-beta-naltrexol. The derivatized extracts are analyzed by monitoring ion currents at m/z 633 (naltrexone), m/z 636 (naltrexone-2H3), m/z 633 6-beta-naltrexol), and m/z 640 (6-beta-naltrexol-2H7). Control plasma samples containing 0.3, 3, or 30 ng/nl of each analyte were analyzed for precision and accuracy with the following results: intra-assay, the percentage of target concentrations were 107-113% for naltrexone and 107-120% for 6-beta-naltrexol, and the coefficients of variation (CVs) were 3.1-6.3% for naltrexone and 3.1-5.7% for 6-beta-naltrexol; interassay, the percentage of target concentrations were 103-110% for naltrexone and 110-113% for 6-beta-naltrexol, and the CVs were 6.1-9.1% for naltrexone and 5.9-9.1% for 6-beta-naltrexol. At the limit of quantitation (LOQ) of 0.1 ng/ml, both analytes quantified within 20% of the target concentration with CVs less than 17%. The extraction recoveries determined at 0.3 and 30 ng/ml were 79 and 80% for naltrexone and 76 and 75% for 6-beta-naltrexol. Bench-top stability tested with concentrations of 0.3 and 3.0 ng/ml did not decrease more than 10% from the zero-hour controls at 3, 6 and 24 h. Selectively was determined using plasma from six donors and none showed interfering peaks greater than 22% of the LOQ for naltrexone and 53% of the LOQ for 6-beta-naltrexol. Using this method, naltrexone and 6-beta-naltrexol were readily detected in plasma specimens collected 5.5 h after oral doses of 25 or 100 mg naltrexone. Following discontinuation of treatment, naltrexone was detected 30 h after the 100-mg dose, whereas 6-beta-naltrexol was detected 125 h after both the 25- and 100-mg doses. PMID:9248940

  15. A rapid and accurate method for the determination of plutonium in food using magnetic sector ICP-MS with an ultra-sonic nebuliser and ion chromatography.

    PubMed

    Evans, P; Elahi, S; Lee, K; Fairman, B

    2003-02-01

    In the event of a nuclear incident it is essential that analytical information on the distribution and level of contamination is available. An ICP-MS method is described which can provide data on plutonium contamination in food within 3 h of sample receipt without compromising detection limits or accuracy relative to traditional counting methods. The method can also provide simultaneous determinations of americium and neptunium. Samples were prepared by HNO3 closed-vessel microwave digestion, evaporated to dryness and diluted into a mobile phase comprising 1.5 M HNO3 and 0.1 mM 2,6-pyridinedicarboxylic acid. A commercially available polystyrene-divinylbenzene ion chromatography column provides on-line separation of 239Pu and 238U reducing the impact of the 238U1H interference. Oxidation of the sample using H2O2 ensures all Pu is in the Pu(+4) state. The oxidation also displaces Np away from the solvent front by changing the oxidation state from Np(+3) to Np(+4) and produces the insoluble Am(+4) ion. Simultaneous Pu, Am and Np analyses therefore require omission of the oxidation stage and some loss of Pu data quality. Analyses were performed using a magnetic sector ICP-MS (Finnigan MAT Element). The sample is introduced to the plasma via an ultrasonic nebuliser-desolvation unit (Cetac USN 6000AT+). This combination achieves an instrumental sensitivity of 238U > 2 x 10(7) cps/ppb and removes hydrogen from the sample gas, which also inhibits the formation of 238U1H. The net effect of the improved sample introduction conditions is to achieve detection levels for Pu of 0.020 pg g(-1) (4.6 x 10(-2) Bq kg(-1)) which is significantly below 1/10th of the most stringent EU (European Union) legislation, currently 0.436 pg g(-1) (1 Bq kg(-1)) set for baby food. The new method was evaluated with a range of biological samples ranging from cabbage to milk and meat. Recovery of Pu agrees with published values (100% +/- 20%). PMID:12619774

  16. Determination of aminopolycarboxylic acids at ultra-trace levels by means of online coupling ion exchange chromatography and inductively coupled plasma-mass spectrometry with indirect detection via their Pd(2+)-complexes.

    PubMed

    Nette, David; Seubert, Andreas

    2015-07-16

    A new indirect IC-ICP-MS method for the determination of aminopolycarboxylic acids in water samples is described. It is based on the addition of an excess of Pd(II) to water samples. The analytes are forced into very strong and negatively charged palladium complexes, separated by ion exchange chromatography and detected by their palladium content, utilizing an on-line coupled ICP-MS. This method is suitable to determine the concentration of 8 aminopolycarboxylic acids (nitrilotriacetic acid (NTA), (2-carboxyethyl) iminodiacetic acid (?-ADA), methylglycinediacetic acid (MGDA), 2-hydroxyethyl) ethylenediamine triacetic acid (HEDTA), diethylene triamine pentaacetic acid (DTPA), ethylendiamine tetraacetic acid (EDTA), 1,3-diaminopropane tetraacetic acid (1,3-PDTA) and 1,2-diaminopropane tetraacetic acid (1,2-PDTA) at the ngkg(-1) level. The method is faster and easier than the established gas chromatography (GC)-method ISO 16588:2002 [1] and up to two orders of magnitude more sensitive than the ion pair chromatography based method of DIN 38413-8. Analytic performance is superior to ISO 16588:2002 and the comparability is good. PMID:26073818

  17. Polymer separations by liquid interaction chromatography: principles - prospects - limitations.

    PubMed

    Radke, Wolfgang

    2014-03-28

    Most heterogeneities of polymers with respect to different structural features cannot be resolved by only size exclusion chromatography (SEC), the most frequently applied mode of polymer chromatography. Instead, methods of interaction chromatography became increasingly important. However, despite the increasing applications the principles and potential of polymer interaction chromatography are still often unknown to a large number of polymer scientists. The present review will explain the principles of the different modes of polymer chromatography. Based on selected examples it will be shown which separation techniques can be successfully applied for separations with respect to the different structural features of polymers. PMID:24380654

  18. DRUG METABOLISM AND DISPOSITION Vol. 11, No. 3 249-254 AUTHORS' Version SIMPLE AND ION-PAIR HIGH PERFORMANCE LIQUID CHROMATOGRAPHY AS AN

    E-print Network

    Paris-Sud XI, Université de

    -PAIR HIGH PERFORMANCE LIQUID CHROMATOGRAPHY AS AN IMPROVED ANALYTICAL TOOL FOR CHLORAMPHENICOL METABOLIC and quantitative analysis of [3 H]chloramphenicol (CP) metabolites in rat urine. Complete separation followed profiles. Abbreviations used are: CP, chloramphenicol; TBAP, terbutylammonium phosphate; HSA, heptane

  19. Green chromatography.

    PubMed

    P?otka, Justyna; Tobiszewski, Marek; Sulej, Anna Maria; Kupska, Magdalena; Górecki, Tadeusz; Namie?nik, Jacek

    2013-09-13

    Analysis of organic compounds in samples characterized by different composition of the matrix is very important in many areas. A vast majority of organic compound determinations are performed using gas or liquid chromatographic methods. It is thus very important that these methods have negligible environmental impact. Chromatographic techniques have the potential to be greener at all steps of the analysis, from sample collection and preparation to separation and final determination. The paper summarizes the approaches used to accomplish the goals of green chromatography. While complete elimination of sample preparation would be an ideal approach, it is not always practical. Solventless extraction techniques offer a very good alternative. Where solvents must be used, the focus should be on the minimization of their consumption. The approaches used to make chromatographic separations greener differ depending on the type of chromatography. In gas chromatography it is advisable to move away from using helium as the carrier gas because it is a non-renewable resource. GC separations using low thermal mass technology can be greener because of energy savings offered by this technology. In liquid chromatography the focus should be on the reduction of solvent consumption and replacement of toxic and environmentally hazardous solvents with more benign alternatives. Multidimensional separation techniques have the potential to make the analysis greener in both GC and LC. The environmental impact of the method is often determined by the location of the instrument with respect to the sample collection point. PMID:23932374

  20. Paper Chromatography

    NSDL National Science Digital Library

    Reeves, James H.

    2011-05-19

    This is a site with experiments that provide a brief introduction to the idea of separation of components in a mixture and a set of instructions for students for separating colored compounds by paper chromatography (on coffee filters). The appropriate audience would be students in a high-school or introductory, non major college chemistry class.

  1. This-layer chromatography/electrospray ionization triple-quadrupole linear ion trap mass spectrometry system: analysis of rhodamine dyes separated on reversed-phase C8 plates

    SciTech Connect

    Ford, Michael J [ORNL; Kertesz, Vilmos [ORNL; Van Berkel, Gary J [ORNL

    2005-01-01

    The direct analysis of separated rhodamine dyes on reversed-phase C{sub 8} thin-layer chromatography plates using a surface sampling/electrospray emitter probe coupled with a triple-quadrupole linear ion trap mass spectrometer is presented. This report represents continuing work to advance the performance metrics and utility of this basic surface sampling electrospray mass spectrometry system for the analysis of thin-layer chromatography plates. Experimental results examining the role of sampling probe spray end configuration on liquid aspiration rate and gas-phase ion signal generated are discussed. The detection figures-of-merit afforded by full-scan, automated product ion and selected reaction monitoring modes of operation were examined. The effect of different eluting solvents on mass spectrum signal levels with the reversed-phase C{sub 8} plate was investigated. The combined effect of eluting solvent flow-rate and development lane surface scan rate on preservation of chromatographic resolution was also studied. Analysis of chromatographically separated red pen ink extracts from eight different pens using selected reaction monitoring demonstrated the potential of this surface sampling electrospray mass spectrometry system for targeted compound analysis with real samples.

  2. Determination of glufosinate ammonium and its metabolite (AE F064619 and AE F061517) residues in water by gas chromatography with tandem mass spectrometry after ion exchange cleanup and derivatization.

    PubMed

    Royer, A; Beguin, S; Sochor, H; Communal, P Y

    2000-11-01

    An analytical method for the determination of glufosinate ammonium and its principal metabolites, AE F064619 and AE F061517, in water of two different hardnesses (5 and 30 DH, French hardness) has been developed and validated. Samples were spiked at different levels (0. 05 and 0.5 microgram/L) and were purified by column chromatography on ion-exchange resins. After derivatization with glacial acetic acid and trimethylarthoacetate mixture, the derivatives were quantified by using capillary gas chromatography with an ion-trap tandem mass spectrometric detector. Analytical conditions for MS/MS detection were optimized, and the quantification was carried out on the areas of the most representative ions. The limit of quantification was validated at 0.05 microgram/L for each compound. The mean recovery value and the relative standard deviation (n = 20) were 92.0% and 17. 8% for glufosinate ammonium, 90.2% and 15.8% for AE F064619, and 89. 7% and 12.7% for AE F061517. PMID:11087456

  3. Investigation of the use of immobilised metal affinity chromatography for the on-line sample clean up and pre-concentration of nucleotides prior to their determination by ion pair liquid chromatography-electrospray mass spectrometry: a pilot study

    Microsoft Academic Search

    Robin Tuytten; Filip Lemière; Walter Van Dongen; Herman Slegers; Russell P Newton; Eddy L Esmans

    2004-01-01

    This study explored an alternative way to enrich and pre-purify biological samples containing nucleoside mono-, di- and triphosphates. These compounds were trapped by immobilised metal affinity chromatography (IMAC) on a Poros® 20 MC IMAC-column, which was conditioned with Fe3+. The IMAC-column was implemented in a column switching set-up separating nucleoside mono-, di- and triphosphates on a Hypersil ODS 35mm ×

  4. Displacement chromatography of chemotactic peptides 1 Presented at the 1998 International Symposium on Preparative Chromatography, Ion Exchange, and Adsorption\\/Desorption Processes and Related Techniques, Washington, DC, 31 May–3 June 1998. 1

    Microsoft Academic Search

    Sundar Ramanan; Ajoy Velayudhan

    1999-01-01

    Displacement chromatography was successfully used to separate a binary peptide mixture, n-formyl-Met–Phe and n-formyl-Met–Trp, on a reversed-phase column. Displacement parameters such as choice of displacer, displacer concentration, mobile phase organic level, and flow-rate were critically examined in the context of maximizing productivity. Since the feed composition was limited by solubility, optimal productivity was sought as a function of feed volume.

  5. Simultaneous determination of 18 preservative residues in vegetables by ultra high performance liquid chromatography coupled with triple quadrupole/linear ion trap mass spectrometry using a dispersive-SPE procedure.

    PubMed

    Zhou, Xue; Cao, Shurui; Li, Xianliang; Tang, Bobin; Ding, Xiaowen; Xi, Cunxian; Hu, Jiangtao; Chen, Zhiqiong

    2015-05-01

    A new method combining dispersive-solid phase purification procedure with ultra high performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry was developed for simultaneous determination of 18 preservative residues in vegetables. The new method not only had the advantages of dispersive-solid phase purification procedure such as high recoveries, easy operation, rapid analysis, little solvent usage and wide analysis range of preservatives, but also had the advantages of ultra high performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry to be operated in positive mode and negative mode simultaneously. The method was validated for the following representative matrices: radish (tuber), tomato (eggplant fruit), cabbage (leafy), cowpea (bean), cucumber (melon) and so on. Samples were extracted with hexane-ethyl acetate (1:2, v/v), and then detected by ultra high performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry after being cleaned up with dispersive-solid phase purification procedure. Significant matrix effects were compensated by using the matrix-matched calibration curves. 18 preservatives showed good linearity over the range of 5.0-100.0 ?g/L with correlation coefficients of 0.9904-1.000. The limits of detections were in the range of 0.04-4.16 ?g/kg and the limits of quantity were in the range of 0.13-13.85 ?g/kg. The recoveries of 18 preservatives ranged from 76.0% to 120.0% with the spiked levels of 2, 4 and 10 ?g/kg into homogenized vegetables, and the relative standard deviations (RSDs) ranged from 0.3% to 14.8%. Compared with the reported literatures, the method is more rapid, simple, highly sensitive, reliable and can meet testing requirements of 18 preservative residues in vegetables. PMID:25797719

  6. Determination of free sulfites (SO3-2) in dried fruits processed with sulfur dioxide by ion chromatography through anion exchange column and conductivity detection.

    PubMed

    Liao, Benjamin S; Sram, Jacqueline C; Files, Darin J

    2013-01-01

    A simple and effective anion ion chromatography (IC) method with anion exchange column and conductivity detector has been developed to determine free sulfites (SO3-2) in dried fruits processed with sulfur dioxide. No oxidation agent, such as hydrogen peroxide, is used to convert sulfites to sulfates for IC analysis. In addition, no stabilizing agent, such as formaldehyde, fructose or EDTA, is required during the sample extraction. This method uses aqueous 0.2 N NaOH as the solvent for standard preparation and sample extraction. The sulfites, either prepared from standard sodium sulfite powder or extracted from food samples, are presumed to be unbound SO3-2 in aqueous 0.2 N NaOH (pH > 13), because the bound sulfites in the sample matrix are released at pH > 10. In this study, sulfites in the standard solutions were stable at room temperature (i.e., 15-25 degrees C) for up to 12 days. The lowest standard of the linear calibration curve is set at 1.59 microg/mL SO3-2 (equivalent to 6.36 microg/g sample with no dilution) for analysis of processed dried fruits that would contain high levels (>1000 microg/g) of sulfites. As a consequence, this method typically requires significant dilution of the sample extract. Samples are prepared with a simple procedure of sample compositing, extraction with aqueous 0.2 N NaOH, centrifugation, dilution as needed, and filtration prior to IC. The sulfites in these sample extracts are stable at room temperature for up to 20 h. Using anion IC, the sulfites are eluted under isocratic conditions with 10 mM aqueous sodium carbonate solution as the mobile phase passing through an anion exchange column. The sulfites are easily separated, with an analysis run time of 18 min, regardless of the dried fruit matrix. Recoveries from samples spiked with sodium sulfites were demonstrated to be between 81 and 105% for five different fruit matrixes (apricot, golden grape, white peach, fig, and mango). Overall, this method is simple to perform and effective for the determination of high levels of sulfites in dried fruits. PMID:24282955

  7. Separation, detection, and identification of peptides by ion-pair reversed-phase high-performance liquid chromatography-electrospray ionization mass spectrometry at high and low pH

    Microsoft Academic Search

    Hansjörg Toll; Herbert Oberacher; Remco Swart; Christian G. Huber

    2005-01-01

    Bioactive peptides and tryptic digests of various proteins were separated under acidic and alkaline conditions by ion-pair-reversed-phase high-performance liquid chromatography (RP-HPIPC) in 200?m I.D. monolithic, poly(styrene-divinylbenzene)-based capillary columns using gradients of acetonitrile in 0.050% aqueous trifluoroacetic acid, pH 2.1, or 1.0% triethylamine-acetic acid, pH 10.6. Chromatographic performances with mobile phases of low and high-pH were practically equivalent and facilitated the

  8. Identification and determination of 34 water-soluble synthetic dyes in foodstuff by high performance liquid chromatography-diode array detection-ion trap time-of-flight tandem mass spectrometry.

    PubMed

    Li, Xiu Qin; Zhang, Qing He; Ma, Kang; Li, Hong Mei; Guo, Zhen

    2015-09-01

    An accurate method combining high performance liquid chromatography (HPLC) with diode array detection (DAD) and ion-trap time-of-flight mass spectrometry (IT-TOF/MS) was developed for simultaneous identification and quantification of 34 water-soluble synthetic dyes in foodstuff. Fragmentation patterns of synthetic dyes were proposed based on IT-TOF/MS. The molecular ion [M+H](+) was not observed in the conventional single-stage mass spectra for most of synthetic dyes. The single-stage mass spectra of synthetic dyes all afforded the diagnostic ions [(M-nNa+nH)+H](+) or [(M-nNa+nH)-H](-) in the positive or negative mode. Doubly charged ions were the characteristic ions of azo dyes. An HPLC-DAD method was developed to analyze 34 synthetic dyes in foodstuffs. The limits of detection (LOD) for the dyes were 0.01-0.05 ?g/mL. The recoveries were between 76.1% and 105.0% with a RSD ranging from 1.4% to 6.4%. This method was successfully applied to analyzing the 34 water-soluble synthetic dyes in 21 commercial foods. PMID:25842343

  9. Chromatography Lab

    NSDL National Science Digital Library

    2014-09-18

    To increase students' awareness of possible invisible pollutants in drinking water sources, students perform an exciting lab requiring them to think about how solutions and mixtures exist even in unsuspecting places such as ink. They use alcohol and chromatography paper to separate the components of black and colored marker ink. Students witness first-hand how components of a solution can be separated, even when those individual components are not visible in solution.

  10. Water quality monitoring of Jialing-River in Chongqing using advanced ion chromatographic system.

    PubMed

    Tanaka, Kazuhiko; Shi, Chao-Hong; Nakagoshi, Nobukazu

    2012-04-01

    The water quality monitoring operation to evaluate the water quality of polluted river is an extremely important task for the river-watershed management/control based on the environmental policy. In this study, the novel, simple and convenient water quality monitoring of Jialing-River in Chongqing, China was carried out using an advanced ion chromatography (IC) consisting of ion-exclusion/cation-exchange chromatography (IEC/CEC) with conductivity detection for determining simultaneously the common anions such as SO4(2-), Cl(-), and NO3(-) and the cations such as Na+, NH4+, K+, Mg2+, and Ca2+, the ion-exclusion chromatography (IEC) with visible detection for determining simultaneously the nutrient components such as phosphate and silicate ions, and the IEC with the enhanced conductivity detection using a post column of K+-form cation-exchange resin for determining HCO3(-)-alkalinity as an inorganic-carbon source for biomass synthesis in biological reaction process under the aerobic conditions. According to the ionic balance theory between the total equivalent concentrations of anions and cations, the water quality evaluation of the Jialing-River waters taking at different sampling sites in Chongqing metropolitan area was carried out using the advanced IC system. As a result, the effectiveness of this novel water quality monitoring methodology using the IC system was demonstrated on the several practical applications to a typical biological sewage treatment plant on Jialing-River of Chongqing. PMID:22799189

  11. A NEW SW-846 METHOD FOR THE ANALYSIS OF TOXAPHENE AND TOXAPHENE CONGENERS IN SOLID AND AQUEOUS SAMPLES USING GAS CHROMATOGRAPHY / NEGATIVE ION MASS SPECTROMETRY

    EPA Science Inventory

    US EPA SW-846 methods have typically relied on dual column gas chromatography coupled with electron capture detection (GC-ECD) for analysis of low concentrations of organochlorine pesticides, including toxaphene, in environmental samples. Toxaphene is one of the most widely appl...

  12. Preparation of recombinant murine tumor necrosis factor-? in Escherichia coli: A rapid method to remove tags from fusion proteins by thrombin-cleavage and ion-exchange chromatography

    Microsoft Academic Search

    Hiroki Tsukamoto; Kenji Fukudome; Jun Kohara; Hiroshi Nakatake; Masao Kimoto

    2007-01-01

    A recombinant protein of murine tumor necrosis factor (TNF)-? was expressed in Escherichia coli (E. coli) by using a pET Trx Fusion System. The fusion protein was effectively solubilized and purified by Ni-affinity chromatography. A high concentration of thrombin quickly and specifically cleaved the introduced site between the tags and the target fragment. We found that thrombin tightly bound to

  13. Rapid screening procedures for the hydrolysis products of chemical warfare agents using positive and negative ion liquid chromatography–mass spectrometry with atmospheric pressure chemical ionisation

    Microsoft Academic Search

    Robert W Read; Robin M Black

    1999-01-01

    Qualitative screening procedures have been developed for the rapid detection and identification of the hydrolysis products of chemical warfare agents in aqueous samples and extracts, using liquid chromatography–mass spectrometry with positive and negative atmospheric pressure chemical ionisation (APCI). Previously reported screening procedures, which used positive APCI or electrospray ionisation (ESI), were modified by using LC conditions that allowed acquisition of

  14. Rapid procedure for plutonium and uranium determination in soils using a borate fusion followed by ion-exchange and extraction chromatography

    Microsoft Academic Search

    Ian Croudace; Phillip Warwick; Rex Taylor; Stephen Dee

    1998-01-01

    A rapid and highly precise method, which uses a borate fusion, of U and Pu determination in soils, sediments and other materials is described. The chemical separation steps are optimised by using an anion resin column stacked on an extraction chromatography column (Eichrom Industries UTEVA resin). The whole procedure was streamlined to measure 700 soil samples in 10 weeks as

  15. PULSED POSITIVE ION NEGATIVE ION CHEMICAL IONIZATION MASS SPECTROMETRIC APPLICATONS TO ENVIRONMENTAL AND HAZARDOUS WASTE ANALYSIS

    EPA Science Inventory

    The simultaneous acquisition of both positive ion and negative ion data under chemical ionization mass spectrometric conditions can aid in the confirmation of assignments made by electron impact gas chromatography mass spectrometry or electron capture gas chromatography. Pulsed p...

  16. Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of pesticides in water by C-18 solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selected-ion monitoring

    USGS Publications Warehouse

    Zaugg, Steven D.; Sandstrom, Mark W.; Smith, Steven G.; Fehlberg, Kevin M.

    1995-01-01

    A method for the isolation of 41 pesticides and pesticide metabolites in natural-water samples using C-18 solid-phase extraction and determination by capillary-column gas chromatography/mass spectrometry with selected-ion monitoring is described. Water samples are filtered to remove suspended particulate matter and then are pumped through disposable solid-phase extraction columns containing octadecyl-bonded porous silica to extract the pesticides. The columns are dried using carbon dioxide or nitrogen gas, and adsorbed pesticides are removed from the columns by elution with 3.0 milliliters of hexane-isopropanol (3:1). Extracted pesticides are determined by capillary- column gas chromatography/mass spectrometry with selected-ion monitoring of three characteristic ions. The upper concentration limit is 4 micrograms per liter (g/L) for most pesticides, with the exception of widely used corn herbicides--atrazine, alachlor, cyanazine, and metolachlor--which have upper concentration limits of 20 g/L. Single- operator method detection limits in reagent-water samples range from 0.001 to 0.018 g/L. Average short-term single-operator precision in reagent- water samples is 7 percent at the 0.1- and 1.0-g/L levels and 8 percent at the 0.01-g/L level. Mean recoveries in reagent-water samples are 73 percent at the 0.1- and 1.0-g/L levels and 83 percent at the 0.01-g/L level. The estimated holding time for pesticides after extraction on the solid-phase extraction columns was 7 days. An optional on-site extraction procedure allows for samples to be collected and processed at remote sites where it is difficult to ship samples to the laboratory within the recommended pre-extraction holding time.

  17. LIQUID CHROMATOGRAPHY\\/POSITIVE-ION ELECTROSPRAY TANDEM MASS SPECTROMETRY ASSAY FOR NISOLDIPINE IN HUMAN PLASMA AND ITS APPLICATION TO A PHARMACOKINETIC STUDY

    Microsoft Academic Search

    Renwang Liu; Zenghui Teng; Chengjun Yuan; Menglei Huan; Xinyou Liu; Siyuan Zhou

    2011-01-01

    A rapid, sensitive, and specific method was developed for the identification and quantitation of the calcium antagonist nisoldipine in human plasma by liquid chromatography coupled with tandem mass spectrometry using nimodipine as an internal standard. Nisoldipine was extracted from human plasma (0.2 mL) by a liquid\\/liquid procedure using diethyl ether as the eluent. The mass spectrometer was operated in the multiple

  18. Study on the photocatalytic degradation of methyl orange in water using Ag\\/ZnO as catalyst by liquid chromatography electrospray ionization ion-trap mass spectrometry

    Microsoft Academic Search

    Tianwen Chen; Yuanhui Zheng; Jin-Ming Lin; Guonan Chen

    2008-01-01

    A nanocrystal catalyst Ag\\/ZnO was successfully synthesized using a simple solvothermal method in this study. This catalyst\\u000a was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that this catalyst\\u000a was composed of metallic Ag and ZnO. The photodegradation of methyl orange (MO) was investigated in aqueous suspension containing\\u000a Ag\\/ZnO catalyst under UV irradiation. Liquid chromatography

  19. Nanofluidic Size-Exclusion Chromatograph

    NASA Technical Reports Server (NTRS)

    Feldman, Sabrina; Svehla, Danielle; Grunthaner, Frank; Feldman, Jason; Shakkottai, P.

    2004-01-01

    Efforts are under way to develop a nanofluidic size-exclusion chromatograph (SEC), which would be a compact, robust, lightweight instrument for separating molecules of interest according to their sizes and measuring their relative abundances in small samples. About as large as a deck of playing cards, the nanofluidic SEC would serve, in effect, as a laboratory on a chip that would perform the functions of a much larger, conventional, bench-top SEC and ancillary equipment, while consuming much less power and much smaller quantities of reagent and sample materials. Its compactness and low power demand would render it attractive for field applications in which, typically, it would be used to identify and quantitate a broad range of polar and nonpolar organic compounds in soil, ice, and water samples. Size-exclusion chromatography is a special case of high-performance liquid chromatography. In a conventional SEC, a sample plug is driven by pressure along a column packed with silica or polymer beads that contain uniform nanopores. The interstices between, and the pores in, the beads collectively constitute a size-exclusion network. Molecules follow different paths through the size-exclusion network, such that characteristic elution times can be related to sizes of molecules: basically, smaller molecules reach the downstream end of the column after the larger ones do because the smaller ones enter minor pores and stay there for a while, whereas the larger ones do not enter the pores. The volume accessible to molecules gradually diminishes as their size increases. All molecules bigger than a pore size elute together. For most substances, the elution times and sizes of molecules can be correlated directly with molecular weights. Hence, by measuring the flux of molecules arriving at the downstream end as a function of time, one can obtain a liquid mass spectrum for the molecules present in a sample over a broad range of molecular weights.

  20. High-Resolution Twin-Ion Metabolite Extraction (HiTIME) Mass Spectrometry: Nontargeted Detection of Unknown Drug Metabolites by Isotope Labeling, Liquid Chromatography Mass Spectrometry, and Automated High-Performance Computing.

    PubMed

    Leeming, Michael G; Isaac, Andrew P; Pope, Bernard J; Cranswick, Noel; Wright, Christine E; Ziogas, James; O'Hair, Richard A J; Donald, William A

    2015-04-21

    The metabolic fate of a compound can often determine the success of a new drug lead. Thus, significant effort is directed toward identifying the metabolites formed from a given molecule. Here, an automated and nontargeted procedure is introduced for detecting drug metabolites without authentic metabolite standards via the use of stable isotope labeling, liquid chromatography mass spectrometry (LC/MS), and high-performance computing. LC/MS of blood plasma extracts from rats that were administered a 1:1 mixture of acetaminophen (APAP) and (13)C6-APAP resulted in mass spectra that contained "twin" ions for drug metabolites that were not detected in control spectra (i.e., no APAP administered). Because of the development of a program (high-resolution twin-ion metabolite extraction; HiTIME) that can identify twin-ions in high-resolution mass spectra without centroiding (i.e., reduction of mass spectral peaks to single data points), 9 doublets corresponding to APAP metabolites were identified. This is nearly twice that obtained by use of existing programs that make use of centroiding to reduce computational cost under these conditions with a quadrupole time-of-flight mass spectrometer. By a manual search for all reported APAP metabolite ions, no additional twin-ion signals were assigned. These data indicate that all the major metabolites of APAP and multiple low-abundance metabolites (e.g., acetaminophen hydroxy- and methoxysulfate) that are rarely reported were detected. This methodology can be used to detect drug metabolites without prior knowledge of their identity. HiTIME is freely available from https://github.com/bjpop/HiTIME . PMID:25818563

  1. Off-line combination of reversed-phase liquid chromatography and laser desorption/ionization time-of-flight mass spectrometry with seamless post-source decay fragment ion analysis for characterization of square-planar nickel(II) complexes.

    PubMed

    Rehulka, Pavel; Popkov, Alexander; Nádvorník, Milan; Planeta, Josef; Mazanec, Karel; Chmelík, Josef

    2006-04-01

    Characterization of square-planar nickel(II) complexes of the Schiff base of (S)-N-benzylproline (2-benzoylphenyl)amide and various amino acids that are used as efficient alpha-amino acids synthons was carried out using laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS) in off-line combination with liquid chromatography. A mixture of four square-planar nickel(II) complexes was separated using reversed-phase liquid chromatography (RPLC) and the separated fractions from the chromatographic run were spotted on the metal target directly from the column outlet using a lab-made sample deposition device. The separated fractions were then analyzed by LDI-TOF MS. Seamless postsource decay (sPSD) fragment ion analysis was used for their structural characterization, which made possible the confirmation of expected chemical structures of the analyzed compounds. The off-line combination of the separation by RPLC and analysis by LDI-TOF MS allowed successful separation, sensitive detection and structure elucidation of the square-planar nickel(II) complexes. PMID:16453277

  2. Characterization and quantitative analysis of phenylpropanoid amides in eggplant (Solanum melongena L.) by high performance liquid chromatography coupled with diode array detection and hybrid ion trap time-of-flight mass spectrometry.

    PubMed

    Sun, Jing; Song, Yue-Lin; Zhang, Jing; Huang, Zheng; Huo, Hui-Xia; Zheng, Jiao; Zhang, Qian; Zhao, Yun-Fang; Li, Jun; Tu, Peng-Fei

    2015-04-01

    Eggplant (Solanum melongena L.) is a famous edible and medicinal plant. Despite being widely cultivated and used, data on certain parts other than the fruit are limited. The present study focused on the qualitative and quantitative analysis of the chemical constituents, particularly phenylpropanoid amides (PAs), in eggplant. The mass fragmentation patterns of PAs were proposed using seven authentic compounds with the assistance of a hybrid ion trap time-of-flight mass spectrometer. Thirty-seven compounds (27 PAs and 10 others) were detected and plausibly assigned in the different parts of eggplant. Afterward, a reliable method based on liquid chromatography coupled with diode array detection was developed, validated, and applied for the simultaneous determination of seven PAs and three caffeoylquinic acids in 17 batches of eggplant roots with satisfactory accuracy, precision, and reproducibility, which could not only provide global chemical insight of eggplant but also offer a reliable tool for quality control. PMID:25796999

  3. Authentication of pineapple (Ananas comosus [L.] Merr.) fruit maturity stages by quantitative analysis of ?- and ?-lactones using headspace solid-phase microextraction and chirospecific gas chromatography-selected ion monitoring mass spectrometry (HS-SPME-GC-SIM-MS).

    PubMed

    Steingass, Christof B; Langen, Johannes; Carle, Reinhold; Schmarr, Hans-Georg

    2015-02-01

    Headspace solid phase microextraction and chirospecific gas chromatography-mass spectrometry in selected ion monitoring mode (HS-SPME-GC-SIM-MS) allowed quantitative determination of ?-lactones (?-C8, ?-C10) and ?-lactones (?-C6, ?-C8, ?-C10). A stable isotope dilution assay (SIDA) with d7-?-decalactone as internal standard was used for quantitative analysis of pineapple lactones that was performed at three progressing post-harvest stages of fully ripe air-freighted and green-ripe sea-freighted fruits, covering the relevant shelf-life of the fruits. Fresh pineapples harvested at full maturity were characterised by ?-C6 of high enantiomeric purity remaining stable during the whole post-harvest period. In contrast, the enantiomeric purity of ?-C6 significantly decreased during post-harvest storage of sea-freighted pineapples. The biogenetical background and the potential of chirospecific analysis of lactones for authentication and quality evaluation of fresh pineapple fruits are discussed. PMID:25172740

  4. Structural identification of the metabolites of ganoderic acid B from Ganoderma lucidum in rats based on liquid chromatography coupled with electrospray ionization hybrid ion trap and time-of-flight mass spectrometry.

    PubMed

    Guo, Xiaoyu; Shen, Xuan; Long, Jie; Han, Jian; Che, Qingming

    2013-09-01

    Ganoderic acid B (GAB), a representative triterpenoid in Ganoderma lucidum, possesses various pharmaceutical effects and has been used as a chemical marker in quality control of G. lucidum and related products. The metabolites of GAB in vivo after its oral administration to rats were investigated by liquid chromatography coupled with electrospray ionization hybrid ion trap and time-of-flight mass spectrometry. A total of 14 metabolites of GAB in rat plasma, bile and various organs were detected and identified by direct comparison with the authentic compounds and their characteristic mass fragmentation patterns. The results showed that oxidization and hydroxylation were the common metabolic pathways for GAB in rats. Moreover, some reduction metabolites of GAB were detected in rat kidney and stomach and glucuronidation only appeared in rat bile. This is the first report on the metabolites of GAB in vivo. PMID:23723086

  5. Comparative investigation of disposition of 3,4-(methylenedioxy)methamphetamine (MDMA) in the rat and the mouse by a capillary gas chromatography-mass spectrometry assay based on perfluorotributylamine-enhanced ammonia positive ion chemical ionization.

    PubMed

    Lim, H K; Zeng, S; Chei, D M; Foltz, R L

    1992-09-01

    A gas chromatography-mass spectrometry assay based on perfluorotributylamine-enhanced ammonia positive ion chemical ionization has been developed for MDMA and three of its primary metabolites in biological specimens; the assay is linear from 2 to 1000 ng ml-1. Quantitatively, more of an administered dose of 10 mg kg-1 MDMA was excreted by the mouse (72%) than by the rat (35%); most in both species was excreted in urine and within 24 h. The difference in per cent excretion is entirely due to proportionally greater excretion of the parent drug by the mouse. 4-Hydroxy-3-methoxymethamphetamine (HMM) is the major urinary metabolite in both species. HMM and another primary metabolite, 4-hydroxy-3-methoxyamphetamine (HMA), were excreted mainly as glucuronide and sulphate conjugates (> 85%). PMID:1363061

  6. Ion interaction reagent reversed-phase high-performance liquid chromatography determination of anti-tuberculosis drugs and metabolites in biological fluids

    Microsoft Academic Search

    M. C Gennaro; R Calvino; C Abrigo

    2001-01-01

    New methods of ion interaction reagent (IIR) RP-HPLC are presented for the determination of anti-tuberculosis drugs and their metabolites, singly or in multi-component mixtures, in biological fluids. The following analytes are considered: isoniazid, ethionamide, pyrazinamide, morphazinamide, p-aminosalicylic acid, nicotinic and isonicotinic acids. Aqueous solutions of three different ion interaction reagents are alternatively or comparatively used as the mobile phases, namely:

  7. Analysis of C(14)-C(17) Polychloro-n-alkanes in Environmental Matrixes by Accelerated Solvent Extraction-High-Resolution Gas Chromatography/Electron Capture Negative Ion High-Resolution Mass Spectrometry.

    PubMed

    Tomy, G T; Stern, G A

    1999-11-01

    A method for quantifying medium-chain (C(14)-C(17)) polychloroalkanes (mPCAs) in environmental matrixes by accelerated solvent extraction high-resolution gas chromatography/electron capture negative ion high-resolution mass spectrometry in the selected ion monitoring mode is presented. The formula group abundance profiles of industrial mPCA mixtures, which are used as standards, and of samples are first determined by monitoring [M - Cl](-) ions of specific m/z values corresponding to the molecular formulas present and by correcting the integrated ion signals for the fractional abundance of the specific m/z value monitored and the number of chlorine atoms in the formula group. mPCA concentrations in environmental samples are then determined by comparing the response of a specific m/z peak in the sample to that in the standard. Extraction recoveries of mPCAs from spiked fish and sodium sulfate (in place of sediment) were >79%. Method detection limits were 13 ng/g for fish and 1.4 ng/?L for sediment, while the analytical detection limit was ?200 pg, at a signal-to-noise ratio of 4:1. By this method, mPCAs were detected in biota and sediment from the mouth of the Detroit River (MI) and ranged from 70 to 900 ng/g. The simultaneous quantitation of C(10)-C(13) (sPCAs) and C(14)-C(17) PCAs, based on monitoring two specific m/z peaks, one characteristic of sPCAs and the other of mPCAs, is also demonstrated. PMID:21662834

  8. Chemical Profiling of Re-Du-Ning Injection by Ultra-Performance Liquid Chromatography Coupled with Electrospray Ionization Tandem Quadrupole Time-of-Flight Mass Spectrometry through the Screening of Diagnostic Ions in MSE Mode

    PubMed Central

    Wang, Zhenzhong; Geng, Jianliang; Dai, Yi; Xiao, Wei; Yao, Xinsheng

    2015-01-01

    The broad applications and mechanism explorations of traditional Chinese medicine prescriptions (TCMPs) require a clear understanding of TCMP chemical constituents. In the present study, we describe an efficient and universally applicable analytical approach based on ultra-performance liquid chromatography coupled to electrospray ionization tandem quadrupole time-of-flight mass spectrometry (UPLC-ESI-Q/TOF-MS) with the MSE (E denotes collision energy) data acquisition mode, which allowed the rapid separation and reliable determination of TCMP chemical constituents. By monitoring diagnostic ions in the high energy function of MSE, target peaks of analogous compounds in TCMPs could be rapidly screened and identified. “Re-Du-Ning” injection (RDN), a eutherapeutic traditional Chinese medicine injection (TCMI) that has been widely used to reduce fever caused by viral infections in clinical practice, was studied as an example. In total, 90 compounds, including five new iridoids and one new sesquiterpene, were identified or tentatively characterized by accurate mass measurements within 5 ppm error. This analysis was accompanied by MS fragmentation and reference standard comparison analyses. Furthermore, the herbal sources of these compounds were unambiguously confirmed by comparing the extracted ion chromatograms (EICs) of RDN and ingredient herbal extracts. Our work provides a certain foundation for further studies of RDN. Moreover, the analytical approach developed herein has proven to be generally applicable for profiling the chemical constituents in TCMPs and other complicated mixtures. PMID:25875968

  9. An automated method for the analysis of phenolic acids in plasma based on ion-pairing micro-extraction coupled on-line to gas chromatography/mass spectrometry with in-liner derivatisation.

    PubMed

    Peters, Sonja; Kaal, Erwin; Horsting, Iwan; Janssen, Hans-Gerd

    2012-02-24

    A new method is presented for the analysis of phenolic acids in plasma based on ion-pairing 'Micro-extraction in packed sorbent' (MEPS) coupled on-line to in-liner derivatisation-gas chromatography-mass spectrometry (GC-MS). The ion-pairing reagent served a dual purpose. It was used both to improve extraction yields of the more polar analytes and as the methyl donor in the automated in-liner derivatisation method. In this way, a fully automated procedure for the extraction, derivatisation and injection of a wide range of phenolic acids in plasma samples has been obtained. An extensive optimisation of the extraction and derivatisation procedure has been performed. The entire method showed excellent repeatabilities of under 10% and linearities of 0.99 or better for all phenolic acids. The limits of detection of the optimised method for the majority of phenolic acids were 10ng/mL or lower with three phenolic acids having less-favourable detection limits of around 100 ng/mL. Finally, the newly developed method has been applied in a human intervention trial in which the bioavailability of polyphenols from wine and tea was studied. Forty plasma samples could be analysed within 24h in a fully automated method including sample extraction, derivatisation and gas chromatographic analysis. PMID:22099223

  10. Automated analysis of low-molecular weight organic acids in ambient air by a microporous tube diffusion scrubber system coupled to ion chromatography

    Microsoft Academic Search

    Yukio Suzuki

    1997-01-01

    A method for the automatic analysis of low-molecular weight organic acids (C) in the atmosphere was developed using a microporous tube coupled to an ion chromatograph. A 220 cm long microporous polytetrafluoroethylene (PTFE) tube provided high collection efficiencies of alkanoic acids (formic acid: 97%, acetic acid: 94%, propionic acid: 92%) and alkenoic acids (vinylacetic acid: 98% and methacrylic acid: 96%).

  11. [Application of simultaneous determination of inorganic ionic species by advanced ion chromatography for water quality monitoring of river water and wastewater].

    PubMed

    Nakatani, Nobutake; Kozaki, Daisuke; Tanaka, Kazuhiko

    2012-04-01

    In this study, our recent work on advanced ion chromatographic methods for the simultaneous determination of inorganic ionic species such as common anions (SO4(2-), Cl(-) and NO3(-)) and cations (Na+, NH4+, K+, Mg2+, and Ca2+), nutrients (phosphate and silicate) and hydrogen ion/alkalinity are summarized first. Then, the applications using these methods for monitoring environmental water quality are also presented. For the determination of common anions and cations with nutrients, the separation was successfully performed by a polymethacrylate-based weakly acidic cation-exchange column of TSKgel Super IC-A/C (Tosoh, 150 mm x 6.0 mm i. d.) and a mixture solution of 100 mmol/L ascorbic acid and 4 mmol/L 18-crown-6 as acidic eluent with dual detection of conductivity and spectrophotometry. For the determination of hydrogen ion/alkalinity, the separation was conducted by TSKgel ODS-100Z column (Tosoh, 150 mm x 4.5 mm i. d.) modified with lithium dodecylsulfate and an eluent of 40 mmol/L LiCl/0.1 mmol/L lithium dodecylsulfate/0.05 mmol/L H2SO4 with conductivity detector. The differences of ion concentration between untreated and treated wastewater showed the variation of ionic species during biological treatment process in a sewage treatment plant. Occurrence and distribution of water-quality conditions were related to the bioavailability and human activity in watershed. From these results, our advanced ion chromatographic methods have contributed significantly for water quality monitoring of environmental waters. PMID:22799192

  12. Targeted analysis of multiple pharmaceuticals, plant toxins and other secondary metabolites in herbal dietary supplements by ultra-high performance liquid chromatography-quadrupole-orbital ion trap mass spectrometry.

    PubMed

    Vaclavik, Lukas; Krynitsky, Alexander J; Rader, Jeanne I

    2014-01-31

    In this study, an ultra-high performance liquid chromatography-quadrupole-orbital ion trap mass spectrometry (UHPLC-Q-orbitrap MS) method was developed and validated for simultaneous determination of 96 pharmaceuticals, plant toxins, and other plant secondary metabolites in herbal dietary supplements. Target analytes were extracted from samples using the QuEChERS (quick easy cheap effective rugged safe) procedure. The instrument was operated in full MS-data dependent tandem mass spectrometry (full MS-dd-MS/MS) acquisition mode which enabled collection of quantitative high resolution (HR) full mass spectral data and confirmatory HR MS/MS data in a single run. The method provided excellent selectivity in both full MS and dd-MS/MS mode. Under optimized collision energy settings, product ion spectra containing both precursor and two or more product ions were obtained for most of the analytes. Limits of detection (LODs) and limits of quantification (LOQs) for the method differed significantly for the examined matrices. LODs?10?g kg(-1) and LOQs?50?g kg(-1) were obtained for 48 to 81% of target compounds across five different matrices. With the exception of highly polar analytes, the optimized QuEChERS extraction procedure provided acceptable recoveries in the range 70%-120%. The precision of the method, characterized as the relative standard deviation (RSD, n=5), was ?25% and ?18% at spiking concentrations of 50?g kg(-1) and 500?g kg(-1), respectively. Because of variations in matrix effects in extracts of herbal dietary supplements that differed in composition, the method of standard additions and an approach based on dilution of matrix components followed by quantification using solvent standards were applied for quantification. The procedure was used to examine commercial dietary supplements for the 96 analytes of interest. To the best of our knowledge, this is the first report of an integrated analysis and quantification of this wide range of compounds. PMID:24439505

  13. Determination of paraquat in human blood plasma using reversed-phase ion-pair high-performance liquid chromatography with direct sample injection

    Microsoft Academic Search

    M. R. Brunetto; A. R. Morales; M. Gallignani; J. L. Burguera; M. Burguera

    2003-01-01

    This report describes the determination of paraquat (PQ) in human blood plasma samples by a direct-injection reversed-phase ion-pair chromatographic method. Blood plasma filtrate was injected directly into the LiChrospher® RP-18 alkyl-diol silica (ADS) precolumn integrated in a column switching system using a mixture of 3% 2-propanol and 10 mM sodium octane sulfonate (SOS) in a 0.05 M phosphate buffer (pH

  14. Determination of mercury and methylmercury in seafood by ion chromatography using photo-induced chemical vapor generation atomic fluorescence spectrometric detection

    Microsoft Academic Search

    Qingyang Liu

    2010-01-01

    A novel method based on photo-induced chemical vapor generation (CVG) as interface to on-line coupled Hg-cysteine ion chromatograpy (IC) with atomic fluorescence spectrometry (AFS) was developed for rapid determination of methylmercury (MHg) in seafood. Separation of inorganic mercury (Hg2+) and methylmercury(CH3Hg+) was accomplished on a Hamilton PRP X-200 polymer-based exchange column with a mobile of 3% acetonitrile, 1% (w\\/w) L-cysteine

  15. Direct characterization of isoquinoline alkaloids in a crude plant extract by ion-pair liquid chromatography–electrospray ionization tandem mass spectrometry: example of Eschscholtzia californica

    Microsoft Academic Search

    Nicolas Fabre; Catherine Claparols; Suzanne Richelme; Marie-Laure Angelin; Isabelle Fourasté; Claude Moulis

    2000-01-01

    An ion-pair HPLC–ESI-MS–MS method has been developed for the direct and rapid characterization of isoquinoline alkaloids in a crudely purified extract of the aerial parts of Eschscholtzia californica (Papaveraceae). This plant was chosen because of its increasing use in pharmaceutical industries and because its well known alkaloid composition allows the optimization of the experimental procedure through an on-line analytical sequence.

  16. Applying Simple Chromatography

    NSDL National Science Digital Library

    John Eichinger

    2009-05-15

    This activity involves chemistry, mystery, colors, and measurement. Students observe the composition of various inks by separating them via water-based chromatography. Students use what they learn about chromatography to solve a mystery involving a suspic

  17. Basic Principles of Chromatography

    NASA Astrophysics Data System (ADS)

    Ismail, Baraem; Nielsen, S. Suzanne

    Chromatography has a great impact on all areas of analysis and, therefore, on the progress of science in general. Chromatography differs from other methods of separation in that a wide variety of materials, equipment, and techniques can be used. [Readers are referred to references (1-19) for general and specific information on chromatography.]. This chapter will focus on the principles of chromatography, mainly liquid chromatography (LC). Detailed principles and applications of gas chromatography (GC) will be discussed in Chap. 29. In view of its widespread use and applications, high-performance liquid chromatography (HPLC) will be discussed in a separate chapter (Chap. 28). The general principles of extraction are first described as a basis for understanding chromatography.

  18. Separation of lanthanide series elements in marine Fe-Mn crusts by ion-exchange chromatography and determination by ICP/AES

    SciTech Connect

    De Carlo, E.H. (Univ. of Hawaii, Honolulu (USA))

    1990-05-01

    A method is described for the separation of lanthanide series elements (REE) from major matrix components of deep-sea ferromanganese crusts using cation-exchange chromatography. The samples are digested in concentrated mineral acids, evaporated to near dryness, and redissolved in 0.5 N HCl. Solutions are passed through Bio-Rad AG50W-X8 strong cation-exchange resin in the H{sup +} form. Major (Fe and Mn) and minor constituents (Al, Co, Cu, Ni, Ca, and Mg) are eluted with 1.7 or 2.0 N HCl; the REE are then eluted from the resin with 4.0 or 6.0 N HCl. Only Ba is not separated and coelutes from the resin with the REE. The method quantitatively separates the lanthanides from most matrix constituents and greatly facilitates their rapid sequential analysis by ICP/AES. The method has been shown to yield accurate and precise analyses of ferromanganese minerals for their REE content in the US Geological Survey standard Fe-Mn nodule A-1 and has been applied to Fe-Mn crusts from their collection.

  19. High-resolution extracted ion chromatography, a new tool for metabolomics and lipidomics using a second-generation orbitrap mass spectrometer

    PubMed Central

    Koulman, Albert; Woffendin, Gary; Narayana, Vinod K; Welchman, Helen; Crone, Catharina; Volmer, Dietrich A

    2009-01-01

    Most analytical methods in metabolomics are based on one of two strategies. The first strategy is aimed at specifically analysing a limited number of known metabolites or compound classes. Alternatively, an unbiased approach can be used for profiling as many features as possible in a given metabolome without prior knowledge of the identity of these features. Using high-resolution mass spectrometry with instruments capable of measuring m/z ratios with sufficiently low mass measurement uncertainties and simultaneous high scan speeds, it is possible to combine these two strategies, allowing unbiased profiling of biological samples and targeted analysis of specific compounds at the same time without compromises. Such high mass accuracy and mass resolving power reduces the number of candidate metabolites occupying the same retention time and m/z ratio space to a minimum. In this study, we demonstrate how targeted analysis of phospholipids as well as unbiased profiling is achievable using a benchtop orbitrap instrument after high-speed reversed-phase chromatography. The ability to apply both strategies in one experiment is an important step forward in comprehensive analysis of the metabolome. Copyright © 2009 John Wiley & Sons, Ltd. PMID:19347970

  20. Chromatography: concepts and contrasts

    SciTech Connect

    Miller, J.M.

    1988-01-01

    As the author states in the Preface, this text attempts to provide a unified approach to chromatography (hence the title) by way of contrasting similarities and differences between gas chromatography (GC), column liquid chromatography (LC), and thin-layer chromatography (TLC). This book is also said to be pitched at an elementary level, suitable for most newcomers to the field (e.g., advanced undergraduates and beginning graduate students in the academic world, as well as bench-level chemists in industry).

  1. 2,6-Pyridinedicarboxylic acid as an eluent for UV and conductivity detection of inorganic anions, magnesium and calcium in water by ion chromatography

    Microsoft Academic Search

    Z. L. Chen; M. A. Adams

    1999-01-01

    Summary  2,6-Pyridinedicarboxylic acid (2,6-PDC) was investigated as an eluent for ion chromatographic (IC) separation of inorganic\\u000a anions, Mg2+ and Ca2+ followed by UV and conductivity detection. Other eluents containing trimesic, pyromellitic and commonly used gluconate\\/borate\\u000a were also studied. Eluents containing 2, 6-PDC gave reasonable resolution and detection sensitivity for all analytes of interest.\\u000a The effects of eluent pH and concentration of

  2. Fractionation of lithium isotopes in cation-exchange chromatography

    Microsoft Academic Search

    Takao Oi; Kazuhiko Kawada; Hidetake Kakihana; Morikazu Hosoe

    2009-01-01

    Various methods for lithium isotope separation have been developed, and their applicability to large-scale enriched lithium isotope production has been assessed. Ion-exchange chromatography is one such method. Cation-exchange chromatography of lithium was carried out to investigate the lithium isotope effect in aqueous ion-exchange systems. The heavier isotope. ⁷Li, was preferentially fractionated into the resin phase in every experiment conducted, and

  3. Determination of free and reversibly bound sulphite in foods by reverse-phase, ion-pairing high-performance liquid chromatography.

    PubMed

    Warner, C R; Daniels, D H; Fitzgerald, M C; Joe, F L; Diachenko, G W

    1990-01-01

    The reaction of sulphite with formaldehyde to form hydroxymethylsulphonate (HMS), which is very stable under the controlled conditions of this assay, was used as the first step in an analytical procedure to determine foodborne sulphite. The effect of mobile-phase pH on the stability of HMS during high-performance liquid chromatography was studied. It was found that on-column HMS dissociation to formaldehyde and bisulphite increased with the pH of the mobile phase; therefore the relatively low pH 4.7, at which the dissociation of HMS was approximately 2%, was selected for the analysis. In addition, the release of sulphite from its reversibly bound forms in wine and other foods was examined as a function of the pH of the extraction medium by following the appearance of HMS formed from the reaction of the freed sulphite with formaldehyde. The rate of dissociation of the reversibly bound sulphite was relatively slow at pH 3 but very rapid at pH 7. This difference in kinetics was exploited to develop a procedure to determine free and reversibly bound sulphite in food. The method was challenged by post-reagent spiking studies, i.e. adding the sulphite spike after the food has been blended with the sulphite-protective formaldehyde solution but before proceeding with the remainder of the assay. An average recovery of 100% with a standard deviation of 5.2% (n = 45) was realized at levels of 5, 10 and 20 ppm by weight as sulphur dioxide. Recovery of the sulphite added as the bisulphite addition product of acetaldehyde, a model compound for reversibly bound sulphite, was 95%. PMID:2174807

  4. Application of ion exchange and extraction chromatography to the separation of actinium from proton-irradiated thorium metal for analytical purposes.

    PubMed

    Radchenko, V; Engle, J W; Wilson, J J; Maassen, J R; Nortier, F M; Taylor, W A; Birnbaum, E R; Hudston, L A; John, K D; Fassbender, M E

    2015-02-01

    Actinium-225 (t1/2=9.92d) is an ?-emitting radionuclide with nuclear properties well-suited for use in targeted alpha therapy (TAT), a powerful treatment method for malignant tumors. Actinium-225 can also be utilized as a generator for (213)Bi (t1/2 45.6 min), which is another valuable candidate for TAT. Actinium-225 can be produced via proton irradiation of thorium metal; however, long-lived (227)Ac (t1/2=21.8a, 99% ?(-), 1% ?) is co-produced during this process and will impact the quality of the final product. Thus, accurate assays are needed to determine the (225)Ac/(227)Ac ratio, which is dependent on beam energy, irradiation time and target design. Accurate actinium assays, in turn, require efficient separation of actinium isotopes from both the Th matrix and highly radioactive activation by-products, especially radiolanthanides formed from proton-induced fission. In this study, we introduce a novel, selective chromatographic technique for the recovery and purification of actinium isotopes from irradiated Th matrices. A two-step sequence of cation exchange and extraction chromatography was implemented. Radiolanthanides were quantitatively removed from Ac, and no non-Ac radionuclidic impurities were detected in the final Ac fraction. An (225)Ac spike added prior to separation was recovered at ? 98%, and Ac decontamination from Th was found to be ? 10(6). The purified actinium fraction allowed for highly accurate (227)Ac determination at analytical scales, i.e., at (227)Ac activities of 1-100 kBq (27 nCi to 2.7 ?Ci). PMID:25596759

  5. Separation and identification of the regioisomers of verdoheme by reversed-phase ion-pair high-performance liquid chromatography, and characterization of their complexes with heme oxygenase.

    PubMed

    Sakamoto, H; Omata, Y; Adachi, Y; Palmer, G; Noguchi, M

    2000-11-01

    We report an HPLC method for separating the four regioisomers of verdoheme formed in the coupled oxidation of hemin with oxygen and ascorbate in aqueous pyridine. The reversed-phase ion-pair system uses hexafluoroacetone and pyridine as ion-pair agents. The regiochemistry of the separated isomers was established both by HPLC of the corresponding biliverdin IX derivatives and by 1H NMR of each isomer. Optical spectra of the pyridine verdohemochrome isomers were similar to each other, but showed differences in the absorption maxima in the red region, which appear at 680, 663, 648 and 660 nm for the alpha, beta, gamma, and delta-isomers, respectively. Each of the four isomers was incorporated anaerobically into heme oxygenase-1, yielding the corresponding verdoheme-enzyme complex. The ferrous forms had absorption maxima at 690, 667, 655, and 663 nm, and their CO-bound forms had maxima at 638, 624, 616, and 626 nm for alpha, beta, gamma, and delta-isomer, respectively. Addition of ferricyanide to the alpha-verdoheme-heme oxygenase complex brought about a ferric low-spin heme-like signal, which is identical with the ferric alpha-verdoheme complexed with the heme oxygenase that was observed in the heme oxygenase reaction. PMID:11132617

  6. Analysis of phosphorus herbicides by ion-pairing reversed-phase liquid chromatography coupled to inductively coupled plasma mass spectrometry with octapole reaction cell.

    PubMed

    Sadi, Baki B M; Vonderheide, Anne P; Caruso, Joseph A

    2004-09-24

    A reversed phase ion-pairing high performance liquid chromatographic (RPIP-HPLC) method is developed for the separation of two phosphorus herbicides, Glufosinate and Glyphosate as well as Aminomethylphosphonic acid (AMPA), the major metabolite of Glyphosate. Tetrabutylammonium hydroxide is used as the ion-pairing reagent in conjunction with an ammonium acetate/acetic acid buffering system at pH 4.7. An inductively coupled plasma mass spectrometer (ICP-MS) is coupled to the chromatographic system to detect the herbicides at m/z = 31P. Historically, phosphorus has been recognized as one of the elements difficult to analyze in argon plasma. This is due to its relatively high ionization potential (10.5 eV) as well as the inherent presence of the polyatomic interferences 14N16O1H+ and 15N16O+ overlapping its only isotope at m/z = 31. An octapole reaction cell is utilized to minimize the isobaric polyatomic interferences and to obtain the highest signal-to-background ratio. Detection limits were found to be in the low ppt range (25-32 ng/l). The developed method is successfully applied to the analysis of water samples collected from the Ohio River and spiked with a standard compounds at a level of 20 microg/l. PMID:15503930

  7. Determination of phosphoric acid mono- and diesters in municipal wastewater by solid-phase extraction and ion-pair liquid chromatography-tandem mass spectrometry.

    PubMed

    Quintana, José Benito; Rodil, Rosario; Reemtsma, Thorsten

    2006-03-01

    The first analytical method for the determination of 13 phosphoric acid mono- and diesters from aqueous samples is presented. The method consists of solid-phase extraction (SPE) and ion-pair liquid chromatographic separation with tri-n-butylamine coupled to electrospray ionization tandem mass spectrometry in the negative ion mode. Due to a lack of pure standards, only 3 of the 13 esters could be quantified. SPE recoveries ranged from 71 to 112% for di-n-butyl phosphate, diphenyl phosphate, and di-(2-ethylhexyl) phosphate (DEHP) with limits of quantification from 7 to 14 ng/L for 100-mL samples. At analyte concentrations >or=1 microg/L, aqueous samples can be analyzed by direct injection without extraction. In municipal wastewater, six diesters and one monoester were unambiguously identified by comparison with synthesized reference material. DEHP showed highest concentrations of 60 and 5 microg/L in raw and treated wastewater, respectively. The detection of monoethylhexyl phosphate was confirmed by LC-Q-TOF-MS analysis, and it was found at a concentration level comparable to DEHP. Laboratory degradation tests show that phosphoric acid diesters can be formed as intermediates in the microbial degradation of trialkyl phosphates that are being used as flame retardants and plasticizers. PMID:16503618

  8. Combined ion-pair extraction and gas chromatography-mass spectrometry for the simultaneous determination of diamines, polyamines and aromatic amines in Port wine and grape juice.

    PubMed

    Fernandes, J O; Ferreira, M A

    2000-07-21

    An accurate and very sensitive method which allows for the simultaneous determination of the diamines (1,3-diaminopropane, putrescine and cadaverine), of the polyamines (spermidine and spermine), and of the aromatic amines (beta-phenylethylamine and tyramine) found in Port wines and corresponding grape juices is presented. Sample clean-up consisted of the extraction of the amines with the ion-pairing reagent bis-2-ethylhexylphosphate dissolved in chloroform followed by a back-extraction with 0.1 M HCl. The hydrochloric extract obtained was dried and the amines were further derivatized with heptafluorobutyric anhydride and analyzed by GC-MS in the selected ion-monitoring mode, with a total run time of 18 min. Under the adopted conditions, the extraction of all the studied compounds was almost complete and the obtained extracts were free of potential interferents present in the samples, namely sugars, and most of the amino acids and polyphenols. Via the use of a set of five selected internal standards (amphetamine, [2H8]putrescine, 1,7-diaminoheptane, norspermidine and norspermine), the data obtained from the linearity, repeatability and recovery experiments were very good for all the compounds assayed. The corresponding limits of detection were invariably below 10 microg l(-1). The method was successfully applied to measure the content of biogenic amines in twelve young and five aged Port wine samples, eleven grape juice samples as well as in ten Portuguese red and white table wines. Results are presented and briefly discussed. PMID:10950286

  9. Integrated Chemical and Microorganism Monitoring of Air Using Gas Chromatography/Ion Mobility Spectometry: Toward an Expanded-Use Volatile Organic Analyzer (VOA)

    NASA Technical Reports Server (NTRS)

    Eiceman, G. A.

    1999-01-01

    The work described in this research program originated with the choice by NASA of an ion mobility spectrometer for air quality monitoring on-board the international spacestation. Though the gas chromatograph-ion mobility spectrometer analyzer known as VOA met or exceeded expectations, limitations in the basic understanding of response and the utilization of foundational principles into usable technology was considered unacceptable. In this research program, a comprehensive model for the origins of mobility spectra was proposed, tested and verified. The principles considered responsible for the appearance of mobility spectra have now been elucidated through this project. This understanding has been applied in automated identification of mobility spectra using neural networks and routine procedures for this now exist. Finally, the limitation on linear range has been shown to be a technical limitation and not a fundamental limitation so that a hardware component was crafted to extend the linear range of a mobility spectrometer by 10X. This project has led to one Ph.D. dissertation and one MS thesis. In addition, over ten public presentations at professional meetings and six journal publications have resulted from this program of research. The findings are so plentiful that total analysis of the findings may require four to six years or more. The findings confirm that the decision to use VOA was sound and that the chemical and physical principles of mobility spectrometry are both understandable and predictable.

  10. Methods development for separation of inorganic anions, organic acids and bases, and neutral organic compounds by ion chromatography and capillary electrophoresis

    SciTech Connect

    Li, J.

    1999-04-01

    A novel anion-exchange resin containing three amine groups was prepared by reaction of a chloromethylated polystyrene-divinylbenzene (PS-DVB) resin with diethylenetriamine. After being protonated by contact with an aqueous acid, this resin can be used for ion chromatographic separation of anions. The charge on the resins can be varied from +1 to +3 by changing the mobile phase pH. The selectivity of the new ion exchangers for various inorganic anions was quite different from that of conventional anion exchangers. The performance of this new anion exchanger was studied by changing the pH and the concentration of the eluent, and several different eluents were used with some common anions as testing analytes. Conductivity detection and UV-visible detection were applied to detect the anions after separation. The new resin can also be used for HPLC separation of neutral organic compounds. Alkylphenols and alkylbenzenes were separated with this new polymeric resin, and excellent separations were obtained under simple conditions. This report contains Chapter 1: General introduction and Chapter 6: General conclusions.

  11. Ballistic protons in incoherent exclusive vector meson production as a measure of rare parton fluctuations at an electron-ion collider.

    PubMed

    Lappi, T; Mäntysaari, H; Venugopalan, R

    2015-02-27

    We argue that the proton multiplicities measured in Roman pot detectors at an electron ion collider can be used to determine centrality classes in incoherent diffractive scattering. Incoherent diffraction probes the fluctuations in the interaction strengths of multiparton Fock states in the nuclear wave functions. In particular, the saturation scale that characterizes this multiparton dynamics is significantly larger in central events relative to minimum bias events. As an application, we study the centrality dependence of incoherent diffractive vector meson production. We identify an observable which is simultaneously very sensitive to centrality triggered parton fluctuations and insensitive to details of the model. PMID:25768758

  12. Ballistic protons in incoherent exclusive vector meson production as a measure of rare parton fluctuations at an Electron-Ion Collider

    E-print Network

    T. Lappi; H. Mäntysaari; R. Venugopalan

    2015-01-22

    We argue that the proton multiplicities measured in Roman pot detectors at an electron ion collider can be used to determine centrality classes in incoherent diffractive scattering. Incoherent diffraction probes the fluctuations in the interaction strengths of multi-parton Fock states in the nuclear wavefunctions. In particular, the saturation scale that characterizes this multi-parton dynamics is significantly larger in central events relative to minimum bias events. As an application, we study the centrality dependence of incoherent diffractive vector meson production. We identify an observable which is simultaneously very sensitive to centrality triggered parton fluctuations and insensitive to details of the model.

  13. Concentration and separation of trace metal ions by reversed-phase adsorption chromatography. [bis(2-hydroxyethyl)dithiocarbamate (HEDC), 1,3-dimethyl-4-acetyl-2-pyrazolin-5-one (DMAP)

    SciTech Connect

    King, J.N.

    1986-01-01

    The concentration and separation of trace metal ions chelated with either bis(2-hydroxyethyl)dithiocarbamate (HEDC) or 1,3-dimethyl-4-acetyl-2-pyrazolin-5-one (DMAP) by reversed-phase adsorption chromatography has been studied. The concentration of metals of the hydrogen sulfide group from very dilute solution by chelation with HEDC and subsequent adsorption on a small column of Amberlite XAD-4 resin is described. Selectivity is achieved by pH adjustment or by the use of masking agents. The metal chelates are eluted from the column with acidic ethanol and determined by AAS. The adsorption properties of five XAD resins and three activated carbons have been studied for removing metal ions chelated with HEDC from industrial wastewater. Amberlite XAD-4 and Nuchar WV-B activated carbon were found to have the highest adsorption capacities. The adsorbents can be regenerated with methanol. The HEDC chelates of Co(III), Cu(II), Ni(II), and Hg(II) have been separated by reversed-phase HPLC. Co(III), Cu(II), and Ni(II) can be determined in the range of 0.005 to 10.0 mg/L, while Hg(II) can be determined in the range of 0.02 to 25 g/L after an on-line preconcentration step. The synthesis and characterization of DMAP is described. The UO2(DMAP)2 chelate has been prepared and characterized. A procedure for concentrating trace amounts of U(VI) chelated with DMAP onto XAD-4 resin is described. 262 refs., 45 figs., 21 tabs.

  14. Journal of Chromatography A, 1042 (2004) 113121 Simultaneous determination of fluoroquinolone, sulfonamide, and

    E-print Network

    Huang, Ching-Hua

    2004-01-01

    Journal of Chromatography A, 1042 (2004) 113­121 Simultaneous determination of fluoroquinolone chromatography­electrospray mass spectrometry Jay E. Renew, Ching-Hua Huang School of Civil and Environmental antibiotics were analyzed using liquid chromatography electrospray mass spectrometry and selected ion

  15. Journal of Chromatography B, 731 (1999) 251260 Simultaneous determination of artemether and its major metabolite

    E-print Network

    Zheng, Mei

    1999-01-01

    Journal of Chromatography B, 731 (1999) 251­260 Simultaneous determination of artemether and its major metabolite dihydroartemisinin in plasma by gas chromatography­mass spectrometry-selected ion- matrices. High-performance liquid chromatography lytical reagent) were obtained from Fisher (Lough- (HPLC

  16. Direct injection ion chromatography for the control of chlorinated drinking water: simultaneous estimation of nine haloacetic acids and quantitation of bromate, chlorite and chlorate along with the major inorganic anions.

    PubMed

    Garcia-Villanova, Rafael J; Raposo Funcia, César; Oliveira Dantas Leite, M Vilani; Toruño Fonseca, Ivania M; Espinosa Nieto, Miguel; Espuelas India, Javier

    2014-09-01

    Most methods for the analysis of haloacetic acids published in recent years are based on ion chromatography with direct injection, employing a gradient elution with potassium hydroxide (KOH). This work reports the exploration of an alternative eluent, a buffer of sodium carbonate/sodium hydrogen carbonate, aimed at the simultaneous analysis of nine haloacetic acids along with bromate, chlorite and chlorate. The alternative of both a less alkaline eluent and a lower temperature of operation may prevent the partial decomposition of some of the haloacetic acids during the analytical process, especially the more vulnerable brominated ones. Gradient elution at temperature of 7 °C yielded the best results, with an acceptable separation of 17 analytes (which includes the major natural inorganic anions) and a good linearity. Precision ranges from 0.3 to 23.4 (% V.C.), and detection limits are within units of ?g L?¹, except for tribromoacetic acid - somewhat high in comparison with those of the official methods. Nonetheless, with the basic instrumentation setup herein described, this method may be suitable for monitoring when the drinking water treatments are to be optimized. This is especially interesting for small communities or for developing/developed countries in which regulations on disinfection by-products others than trihalomethanes are being addressed. PMID:25252348

  17. Polypyrrole/montmorillonite nanocomposite as a new solid phase microextraction fiber combined with gas chromatography-corona discharge ion mobility spectrometry for the simultaneous determination of diazinon and fenthion organophosphorus pesticides.

    PubMed

    Jafari, Mohammad T; Saraji, Mohammad; Sherafatmand, Hossein

    2014-03-01

    A novel solid phase microextraction (SPME) fiber was prepared and coupled with gas chromatography corona discharge ion mobility spectrometry (GC-CD-IMS) based on polypyrrole/montmorillonite nanocomposites for the simultaneous determination of diazinon and fenthion. The nanocomposite polymer was coated using a three-electrode electrochemical system and directly deposited on a Ni-Cr wire by applying a constant potential. The scanning electron microscopy images revealed that the new fiber exhibited a rather porous and homogenous surface. The thermal stability of the fabricated fiber was investigated by thermogravimetric analysis. The effects of different parameters influencing the extraction efficiency such as extraction temperature and time, salt addition, stirring rate, the amount of nanoclay, and desorption temperature were investigated and optimized. The method was exhaustively evaluated in terms of sensitivity, recovery, and reproducibility. The linearity ranges of 0.05-10 and 0.08-10 ?g L(-1), and the detection limits of 0.020 and 0.035 ?g L(-1) were obtained for diazinon and fenthion, respectively. The relative standard deviation values were calculated to be lower than 5% and 8% for intra-day and inter-day, respectively. Finally, the developed method was applied to determine the diazinon and fenthion (as model compounds) in cucumber, lettuce, apple, tap and river water samples. The satisfactory recoveries revealed the capability of the two-dimensional separation technique (retention time in GC and drift time in IMS) for the analysis of complex matrices extracted by SPME. PMID:24528846

  18. Quantitation of deuterated and non-deuterated phenylalanine and tyrosine in human plasma using the selective ion monitoring method with combined gas chromatography-mass spectrometry. Application to the in vivo measurement of phenylalanine-4-monooxygenase activity.

    PubMed

    Zagalak, M J; Curtius, H C; Leimbacher, W; Redweik, U

    1977-11-11

    A specific method is described for the quantitative analysis of deuterated and non-deuterated phenylalanine and tyrosine in human plasma by gas chromatography-mass spectrometry using selective ion monitoring. From the several derivatives investigated, the N- or N,O-trifluoroacetyl methyl esters were found to be the most suitable for our purposes. DL-Phenylalanine-4-d1 and L-tyrosine-d7 were used as internal standards. The sensitivity of this method permits the measurement of amounts as small as ca. 2.5 ng/ml in plasma for both phenylalanine and tyrosine. The coefficients of variation were found to be ca. 1.6% (n = 12) for phenylalanine and 3.0% (n = 12) for tyrosine. Using this method, an in vivo determination of phenylalanine-4-monooxygenase activity in humans is possible by loading the subjects with deuterated L-phenylalanine-d5 (accepted as substrate by phenylalanine-4-monooxygenase E.C. 1.14.16.1) and the subsequent measuring of deuterated L-tyrosine-d4 formed and residual L-phenylalanine-d5. PMID:914934

  19. Screening of key antioxidant compounds of longan (Dimocarpus longan Lour.) seed extract by combining online fishing/knockout, activity evaluation, Fourier transform ion cyclotron resonance mass spectrometry, and high-performance liquid chromatography electrospray ionization mass spectrometry methods.

    PubMed

    Chen, Jinyu; Ge, Zhen-Zhen; Zhu, Wei; Xu, Ze; Li, Chun-Mei

    2014-10-01

    To figure out the key phenolic compounds accounting for the antioxidant effects of longan (Dimocarpus longan Lour.) seed extract, online fishing/knockout method, activity evaluation assays, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), and high-performance liquid chromatography electrospray ionization mass spectrometry (HPLC-ESI-MS) analysis were used jointly for the first time. p-Coumaric acid-glycoside, (S)-flavogallonic acid, ellagic acid derivative, and methyl-ellagic acid glucopyranoside were first identified in longan seeds. In addition, our study revealed that ellagic acid as well as its derivative and p-coumaric acid-glycoside had important contribution to the potent antioxidant activity of longan seed extract, while gallic acid, corilagin, (S)-flavogallonic acid, methyl-ellagic acid glucopyranoside, and ethyl gallate showed very little contribution to the total antioxidant activity of longan seed extract. The combining use of the online fishing/knockout method, activity evaluation assays, FT-ICR-MS, and HPLC-ESI-MS analysis is a useful and simple strategy for screening of key bioactive compounds from complex extracts. PMID:25220361

  20. Metabolism studies of the Kratom alkaloids mitraciliatine and isopaynantheine, diastereomers of the main alkaloids mitragynine and paynantheine, in rat and human urine using liquid chromatography-linear ion trap-mass spectrometry.

    PubMed

    Philipp, Anika A; Wissenbach, Dirk K; Weber, Armin A; Zapp, Josef; Maurer, Hans H

    2011-05-01

    Mitragyna speciosa (Kratom in Thai), native in Southeast Asia, is increasingly misused as a herbal drug of abuse. During metabolism studies on the Kratom alkaloids mitragynine, its diastereomers speciogynine and speciociliatine as well as paynantheine in rats and humans, further isomeric compounds were detected in Kratom users' urine. The question arose whether these compounds were formed from the low abundant, isomeric alkaloids mitraciliatine (MC) and isopaynantheine (ISO-PAY). Therefore, the aim of the presented study was to identify using liquid chromatography-linear ion trap-mass spectrometry their phase I and II metabolites in rat urine after administration of pure MC or ISO-PAY, to confirm their formation in humans, and finally to confirm whether the above-mentioned isomeric compounds in human urine represent MC and ISO-PAY and/or their metabolites. The metabolic pathways of both alkaloids in rats were found to be comparable to those of their corresponding diastereomers. In the human urines tested, not all metabolites found in rats could be detected because of the much lower amounts of MC and ISO-PAY in Kratom. However, all the above-mentioned so far unknown isomeric compounds could be identified in the human urine samples as MC, ISO-PAY and/or their metabolites. The used LC separation was also suitable for the differentiation of all other Kratom alkaloids and their metabolites in human urine. PMID:21450536