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Complex Matrices (complex + matrix)
Selected AbstractsNovel Thorium Membrane Sensors with Anionic Response Based on Trioctylphosphine Oxide and Toluate IonophoresELECTROANALYSIS, Issue 19 2008Abstract Two novel potentiometric polymeric membrane sensors for rapid and accurate determination of thorium are described. These are based on the use of trioctylphosphine oxide (TOPO) and thorium toluate (Th-TA) as ionophores dispersed in poly(vinyl chloride) matrix membranes plasticized with nitrophenyloctyl ether. In strong nitric acid medium, Th(IV) nitrate is converted into [Th(NO3)6]2, complex and sensed as anionic divalent ion which exclude most cationic effect. Validation of the assay methods using the quality assurance standards (linearity range, accuracy, precision, within-day variability, between-day-repeatability, lower detection limit and sensitivity) reveals excellent performance characteristics of both sensors. The sensors exhibit near-Nernstian response for 1.0×10,6,1.0×10,1 M Th over the pH range 2.5,4.5. Calibration slopes of ,32.3±0.3 and ,27.2±0.2,mV/decade, precision of ±0.5 and ±0.8% and accuracy of 98.8±0.9 and 97.9±0.7% are obtained with TOPO and Th-TA based sensors, respectively. Negligible interferences are caused by most interfering mono-, di-, tri-, tetra-, penta-, and hexa-valent elements commonly associated with thorium in naturally occurring minerals and ores. High concentrations of Cl,, F,, SO42,, and NO3, ions have no diverse effect. Complete removal of the effect of the interferents in complex matrices is achieved by retention of [Th(NO3)6]2, complex from 5,M nitric acid/methanol mixture (1,:,9,v/v) on a strong anion exchanger, washing out the cationic interferents followed by stripping off thorium anion complex and measurements. Both sensors are used for determining thorium in certified thorium ore samples (20,120,mg Th/kg) and some naturally occurring ores (200,600,mg Th/kg). The results obtained agree fairly well with the certified labeled values or the data obtained using X-ray fluorescence spectrometry [source] Heavy Metals in Matrices of Food Interest: Sequential Voltammetric Determination at Trace and Ultratrace Level of Copper, Lead, Cadmium, Zinc, Arsenic, Selenium, Manganese and Iron in MealsELECTROANALYSIS, Issue 18 2004Clinio Locatelli Abstract The voltammetric methods are very suitable and versatile techniques for the simultaneous metal determination in complex matrices. The present work, regarding the sequential determination of Cu(II), Pb(II), Cd(II), Zn(II) by square-wave anodic stripping voltammetry (SWASV), As(III), Se(IV) by square-wave cathodic stripping voltammetry (SWCSV) and Mn(II), Fe(III) by square-wave voltammetry (SWV) in matrices involved in foods and food chain as wholemeal, wheat and maize meal, are an interesting example of the possibility to sequentially determine each single element in real samples. Besides the set up of the analytical method, particular attention is aimed either at the problem of possible signal interference or to show that, using the peak area Ap as instrumental datum, it is possible to achieve lower limits of detection. The analytical procedure was verified by the analysis of the standard reference materials: Wholemeal BCR-CRM 189, Wheat Flour NIST-SRM 1567a and Rice Flour NIST-SRM 1568a. Precision, as repeatability, and accuracy, expressed as relative standard deviation and relative error, respectively, were lower than 6% in all cases. In the presence of reciprocal interference, the standard addition method considerably improved the resolution of the voltammetric technique. Once set up on the standard reference materials, the analytical procedure was transferred and applied to commercial meals sampled on market for sale. A critical comparison with spectroscopic measurements is also discussed. [source] Cover Picture: Electrophoresis 13'09ELECTROPHORESIS, Issue 13 2009Article first published online: 20 JUL 200 Issue 13 is a special issue on "CE and CEC of Amino Acids, Peptides and Proteins" assembling 19 papers on various topics including fast, high efficient and high sensitive "CE and CEC techniques for quality control and purity determination of native and (bio)synthetic amino acids, peptides and proteins, for monitoring of their synthesis, isolation, chemical derivatization and enzymatic digestion and also for investigation of their interactions with other molecules. New methodologies, such as electrodialysis for sample preparation, chiral ligand-exchange CE, immunoaffinity CE, affinity capillary isoelectric focusing, combination of transient isotachophoretic preconcentration with capillary zone electophoresis (CZE) analysis, two-dimensional CE-mass spectrometry (MS) separations and advances in high-sensitive CE-laser induced fluorescence (LIF) and CE-electrochemiluminescence detection schemes, are widely presented here. The applications of CE and CEC methods include chiral analysis of amino acids, determination of low abundant amino acids, peptides and proteins in complex matrices, such as human and animal body fluids and tissue biopsies, and profiling of cell lysates and recombinant proteins, e.g. birch pollen allergen and human interleukin 7. As can be seen from several contributions, preparation of new capillary coatings suppressing the adsorption of peptides and proteins to the fused silica capillary wall in their CZE analyses and/or increasing the selectivity of their open-tubular CEC separations remains a hot topic in the area of CE and CEC developments. In addition, it is shown that through the theoretical modelling of the CZE determined effective electrophoretic mobilities of proteins, the important parameters, such as charge, hydration and shape of their molecules, can be estimated." [source] Electrical field-assisted solid-phase extraction coupled on-line to capillary electrophoresis-mass spectrometryELECTROPHORESIS, Issue 10 2008Gabriel Morales-Cid Abstract A substantial demand currently exists for analytical methods affording the determination of very low concentrations of analytes in complex matrices, such as those of environmental and biological samples, as simply as possible. However, the pretreatment of complex samples, which is unavoidable prior to CE-MS analysis, is usually complicated and time-consuming. In this work, we used voltage-assisted SPE for the first time as an alternative to conventional treatments for preconcentrating and purifying analytes. To this end, we used a simple flow system coupled on-line to CE-MS equipment. The system is quite robust and provides reproducible peak areas (the precision ranges from 2.5 to 3.8%). Also, it provides increased sensitivity affording the determination of trace amounts (nanogram per liter levels) of analytes in only a few milliliters of sample. The proposed system was applied to the determination of members of two compound families (viz. tetracyclines and amines). [source] Determination of iodide in samples with complex matrices by hyphenation of capillary isotachophoresis and zone electrophoresisELECTROPHORESIS, Issue 20 2007Pavla Pant Abstract A method has been developed for the determination of iodide in mineral water, seawater, cooking salt, serum, and urine based on hyphenation of capillary ITP and zone electrophoresis. A commercially available instrumentation for capillary ITP with column-switching system was used. ITP served for removal of chloride present in the analyzed samples in a ratio of 106,107:1 to iodide, zone electrophoresis was used for evaluation. Isotachophoretic separation proceeded in a capillary made of fluorinated ethylene,propylene copolymer of 0.8,mm id and 90,mm total length to the bifurcation point filled with a leading electrolyte (LE) composed of 8,mM HCl,+,16,mM ,-alanine (,-Ala),+,10% PVP,+,2.86,mM N2H4×2HCl, pH,3.2; and a terminating electrolyte composed of 8,mM H3PO4,+,16,mM ,-Ala,+,10% PVP,+,5,mM N2H4, pH,3.85 for all the matrices except seawater. For ITP of seawater the LE consisted of 50,mM HCl,+,100,mM ,-Ala,+,10% PVP +,2.86,mM N2H4×2HCl, pH,3.52. Distance of conductivity detector from the injection point and bifurcation point was 52 and 38,mm, respectively. Zone electrophoresis was performed in a capillary made of fused silica of 0.3,mm id and 160,mm total length filled with LE from isotachophoretic step. LODs reached for all matrices were 2,3×10,8,M concentration (2.5,4,,g/L) enabled monitoring of iodide in all analyzed samples with RSD 0.4,9.3%. Estimated concentrations of iodide in individual matrices were 10,6,10,8,M. [source] Importance of the counterion in optimization of a borate electrolyte system for analyses of anions in samples with complex matrices performed by capillary zone electrophoresisELECTROPHORESIS, Issue 20 2004Ludmila K, ivánková Abstract Borate buffers are common background electrolytes for analyses of anions in capillary zone electrophoresis. Usually, sodium borate at a given pH is used and this specification seems to be sufficient for a successful analysis. In this paper, we show that free migration of OH - may deteriorate the analysis of a typical anionic analysis of clinical samples due to uncontrolled migration of OH - throughout the systems of analyzed zones and may damage the stacking of anionic analytes of interest. We have proven that the use of ammonium borate may remedy the situation where the presence of ammonium may selectively stop the free migration of OH - ions, slow down their effective mobility and bring their safe behavior resulting in reproducible stacking of clinically important anions. Results of real analyses of human serum samples confirmed the proposed method and proved that substitution of sodium for ammonium in borate buffers offers reliable analyses of clinical samples having chloride as the bulk component. The experimental results given in this paper are supported also by computer simulation, which can not only support the positive results but also show the dynamics of the separation that is otherwise hidden to any detection possibilities. [source] Rapid screening and characterization of drug metabolites using a new quadrupole,linear ion trap mass spectrometerJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 2 2003Gérard Hopfgartner Abstract The application of a new hybrid RF/DC quadrupole,linear ion trap mass spectrometer to support drug metabolism and pharmacokinetic studies is described. The instrument is based on a quadrupole ion path and is capable of conventional tandem mass spectrometry (MS/MS) as well as several high-sensitivity ion trap MS scans using the final quadrupole as a linear ion trap. Several pharmaceutical compounds, including trocade, remikiren and tolcapone, were used to evaluate the capabilities of the system with positive and negative turbo ionspray, using either information-dependent data acquisition (IDA) or targeted analysis for the screening, identification and quantification of metabolites. Owing to the MS/MS in-space configuration, quadrupole-like CID spectra with ion trap sensitivity can be obtained without the classical low mass cutoff of 3D ion traps. The system also has MS3 capability which allows fragmentation cascades to be followed. The combination of constant neutral loss or precursor ion scan with the enhanced product ion scan was found to be very selective for identifying metabolites at the picogram level in very complex matrices. Owing to the very high cycle time and, depending on the mass range, up to eight different MS experiments could be performed simultaneously without compromising chromatographic performance. Targeted product ion analysis was found to be complementary to IDA, in particular for very low concentrations. Comparable sensitivity was found in enhanced product ion scan and selected reaction monitoring modes. The instrument is particularly suitable for both qualitative and quantitative analysis. Copyright © 2003 John Wiley & Sons, Ltd. [source] High-performance liquid chromatographic determination and pharmacokinetic study of cefepime in goat plasma and milk after pre-column derivatization with Hg(I)JOURNAL OF SEPARATION SCIENCE, JSS, Issue 17-18 2010Nawal A. El-Rabbat Abstract A highly sensitive and selective HPLC method with UV detection was developed for the determination of cefepime in goat plasma and milk. The proposed method was based on the complexation of cefepime with Hg(I) ions that imparts the high selectivity of the proposed method with enhancement of the sensitivity which enabled the analysis of cefepime in complex matrices such as plasma and milk. Detection was performed at 263,nm, using cefuroxime sodium as an internal standard. Chromatographic separation of cefepime and the internal standard was achieved with Aqua RP-C18 column using methanol/triethylamine-acetate buffer, pH 3.5 (18:82, v/v) as mobile phase at a flow rate of 1,mL/min. Linear detector responses were observed spanning the range of 1.3,20,,g/mL. The LOD for standard cefepime was 0.43,,g/mL, whereas the LOD for cefepime in goat plasma was 0.84,,g/mL and the corresponding value in goat milk was 1.1,,g/mL. No interference from endogenous substances in plasma and milk was observed. The developed HPLC method has been successfully applied for the pharmacokinetic study of cefepime in goat plasma and milk, for the first time, after a single intramuscular injection of 50,mg cefepime/kg body weight. [source] Determination of banned Sudan dyes in food samples by molecularly imprinted solid phase extraction-high performance liquid chromatographyJOURNAL OF SEPARATION SCIENCE, JSS, Issue 19 2009Claudio Baggiani Abstract A method for molecularly imprinted SPE of banned Sudan azo-dyes from food samples was investigated. The molecularly imprinted polymer was obtained by suspension polymerization using 1-(4-chlorophenyl)azonaphthalen-2-ol as the mimic template. The molecular recognition properties of imprinted beads were evaluated for use as a SPE sorbent, in order to develop a selective extraction protocol for the Sudan class of dyes. The optimized extraction protocol resulted in a reliable molecularly imprinted SPE (MISPE) method suitable for HPLC analysis. It was selective for the main analyte, Sudan I, and the related azo-dyes Sudan II, III, IV, Sudan Red B, and Sudan Red 7B, while the permitted azo-dyes Allura Red AC, Neococcin, and Sunset Yellow FCF were not extracted. The method was tested for Sudan I, II, III, and IV in five different food samples (hot chilli pepper, hot chilli tomato sauce, sausage, tomato sauce, and hard boiled egg yolk) at three concentration levels (15, 100, and 300 ,g/g). It demonstrated itself to be insensitive to the presence of different complex matrices, precise, accurate, and with good recovery rates (85,101%). The LOD and LOQ were satisfactory for most analytical determinations. [source] Highly sensitive and accurate profiling of carotenoids by supercritical fluid chromatography coupled with mass spectrometryJOURNAL OF SEPARATION SCIENCE, JSS, Issue 9 2009Atsuki Matsubara Abstract We attempted to establish a high-speed and high-resolution profiling method for a carotenoid mixture as a highly selective and highly sensitive detection method; the analysis was carried out by supercritical fluid chromatography (SFC) coupled with mass spectrometry (MS). When an octadecyl-bonded silica (ODS) particle-packed column was used for separation, seven carotenoids including structural isomers were successfully separated within 15 min. This result indicated not only improved separation but also improved throughput compared to the separation and throughput in RP-HPLC. The use of a monolithic ODS column resulted in additional improvement in both the resolution and the throughput; the analysis time was reduced to 4 min by increasing the flow rate. Furthermore, carotenoids in biological samples containing the complex matrices were separated effectively by using several monolithic columns whose back pressure was very low. The mass spectrometer allowed us to perform a more sensitive analysis than UV detection; the detection limit of each carotenoid was 50 pg or below. This is the first report of carotenoid analysis carried out by SFC-MS. The profiling method developed in this study will be a powerful tool for carrying out accurate profiling of biological samples. [source] Time of flight versus ion trap MS coupled to CE to analyse intact proteinsJOURNAL OF SEPARATION SCIENCE, JSS, Issue 10 2008Guillaume L. Erny Abstract In this work, two different CE-MS instruments, namely, CE-ESI-IT-MS and CE-ESI-TOF-MS, applied to analyse intact proteins from complex samples are investigated. The aim of this work was to compare both instruments in terms of LOD, number of proteins detected, and precision and repeatability in the determination of the protein relative molecular mass. Results show that although CE-ESI-IT-MS provides cleaner MS spectra of intact proteins, CE-ESI-TOF-MS allows the identification of a higher number of proteins from complex matrices in an easier way. Performance in terms of peak area reproducibility, LOD and precision in the determination of the molecular mass were similar for both instruments. The usefulness of the optimised CE-ESI-IT-MS and CE-ESI-TOF-MS conditions was demonstrated by studying the zein-proteins composition of three natural maize lines and their corresponding transgenic lines, showing no significant differences. [source] Analysis of flavor and perfume using an internally cooled coated fiber deviceJOURNAL OF SEPARATION SCIENCE, JSS, Issue 7 2007Yong Chen Abstract A miniaturized internally cooled coated fiber device was applied for the analysis of flavors and fragrances from various matrices. Its integration with a CTC CombiPAL autosampler enabled high throughput for the analysis of analytes in complex matrices that required simultaneous heating of the matrices and cooling of the fiber coating to achieve high extraction efficiency. It was found that up to ten times increase of extraction efficiencies was observed when the device was used to extract flavor compounds in water, even when limited sample temperatures were used to preserve the integrity of target compounds. The extraction of the flavor compounds in water with the device was reproducible, with RSD not larger than 15%. The lower limits of the linear ranges were in the low ppb range, which was about one order of magnitude smaller than those obtained with the commercialized 100 ,m PDMS fibers. Exhaustive extraction of some perfume ingredients from a complex matrix (shampoo) was realized. All achieved recoveries were not less than 80%. The repeatability of the extraction of the perfume compounds from shampoo was better than 10%. The linear ranges were about 1,3000 ,g/g, and the LOD was about 0.2,1 ,g/g. The automated internally cooled coated fiber device was demonstrated to be a powerful sample preparation tool in flavor and fragrance analysis. [source] Utilisation of separation methods in the analysis of chemical warfare agentsJOURNAL OF SEPARATION SCIENCE, JSS, Issue 11 2006Barbora Papou Abstract Chemical warfare agents and their degradation products represent a broad group of compounds with different chemical properties (polarity, volatility, thermostability, etc.). These chemicals often have to be detected and determined in complex matrices and therefore highly efficient separation techniques hyphenated to selective and sensitive detectors play an indispensable role. This review offers an overview of selected papers devoted to the title subject. It cannot be considered as a comprehensive literature compilation but should allow the reader to obtain an insight into the application of separation techniques in the important area of human protection and control of chemical weapons. [source] Molecularly imprinted polymers for selective analysis of chemical warfare surrogate and nuclear signature compounds in complex matricesJOURNAL OF SEPARATION SCIENCE, JSS, Issue 11 2005Scott D. Harvey Abstract This paper describes the preparation and evaluation of molecularly imprinted polymers (MIPs) that display specificity toward diisopropyl methylphosphonate (DIMP) and tributyl phosphate (TBP). Polymer activity was assessed by solid-phase extraction and high-performance liquid chromatography experiments. Both DIMP- and TBP-specific vinylpyridine-based MIPs selectively retained their targets relative to a non-imprinted control. Proof-of-principle experiments demonstrated highly selective analysis of the targets from fortified complex matrix samples (diesel fuel, gasoline, and air extract concentrate). The retained MIP fractions gave near quantitative recovery of the target analytes with very low matrix background content. The same fraction from the control sorbent recovered only about half of the analyte and tended to be less pure. [source] Zirconium hydroxide effectively immobilizes and concentrates human enteric virusesLETTERS IN APPLIED MICROBIOLOGY, Issue 5 2002D.H. D'Souza Background: Detection of human enteric viruses in foods and environmental samples requires concentration of viruses from complex matrices before application of molecular or cultural methods. Previous studies have described the use of zirconium hydroxide to concentrate bacteria from clinical, environmental, and food samples. Aims: Our study describes the application of zirconium hydroxide to concentrate human enteric viruses. Methods: Poliovirus type 1, hepatitis A virus (HAV) strain HM-175, and Norwalk virus (NV) were used as models. Virus recovery was evaluated both as loss to discarded supernatants and as recovery in the precipitated pellets. Results: Poliovirus type 1, based on the plaque assay recoveries, ranged from 16 to 59% with minimal loss to the supernatant (1,5%). For both HAV and NV, RT-PCR amplicons of appropriate sizes were detected and confirmed in the pellet fraction with no visible amplicons from the supernatant. Significance and Impact of the Study: This rapid and inexpensive method shows promise as an alternative means to concentrate enteric viruses. [source] Time of flight mass spectrometry applied to the liquid chromatographic analysis of pesticides in water and foodMASS SPECTROMETRY REVIEWS, Issue 6 2006Sílvia Lacorte Abstract Liquid chromatography coupled to mass spectrometry (LC-MS) is an excellent technique to determine trace levels of polar and thermolabile pesticides and their degradation products in complex matrices. LC-MS can be equipped with several mass analyzers, each of which provides unique features capable to identify, quantify, and resolve ambiguities by selecting appropriate ionization and acquisition parameters. We discuss in this review the use of LC coupled to (quadrupole) time-of-flight mass spectrometry (LC-(Q)ToF-MS) to determine the presence of target and non-target pesticides in water and food. This technique is characterized by operating at a resolving power of 10,000 or more. Therefore, it gives accurate masses for both parent and fragment ions and enables the measurement of the elemental formula of a compound achieving compound identification. In addition, the combination of quadrupole-ToF permits tandem mass spectrometry, provides more structural information, and enhances selectivity. The purpose of this article is to provide an overview on the state of art and applicability of liquid chromatography time-of-flight mass spectrometry (LC-ToF-MS), and liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QToF-MS) for the analysis of pesticides in environmental matrices and food. The performance of such techniques is depicted in terms of accurate mass measurement, fragmentation, and selectivity. The final section is devoted to describing the applicability of LC-(Q)ToF-MS to routine analysis of pesticides in food matrices, indicating those operational conditions and criteria used to screen, quantify, and identify target and "suspected" pesticides and their degradation products in water, fruits, and vegetables. The potential and future trends as well as limitations of LC-(Q)ToF-MS for pesticide monitoring are highlighted. © 2006 Wiley Periodicals, Inc. [source] Some remarks on the perturbation of polar decompositions for rectangular matricesNUMERICAL LINEAR ALGEBRA WITH APPLICATIONS, Issue 4 2006Wen Li Abstract In this article we focus on perturbation bounds of unitary polar factors in polar decompositions for rectangular matrices. First we present two absolute perturbation bounds in unitarily invariant norms and in spectral norm, respectively, for any rectangular complex matrices, which improve recent results of Li and Sun (SIAM J. Matrix Anal. Appl. 2003; 25:362,372). Secondly, a new absolute bound for complex matrices of full rank is given. When ,A , Ă,2 , ,A , Ă,F, our bound for complex matrices is the same as in real case. Finally, some asymptotic bounds given by Mathias (SIAM J. Matrix Anal. Appl. 1993; 14:588,593) for both real and complex square matrices are generalized. Copyright © 2005 John Wiley & Sons, Ltd. [source] Specification issues in models of population and employment growth*PAPERS IN REGIONAL SCIENCE, Issue 1 2005Marlon G. Boarnet Spatial econometrics; population and employment growth Abstract., This article examines two specification issues common to spatial econometric population-employment growth models: the specification of the weight matrix and the dynamic stability implied by estimated lag parameters. Using data on Orange County census tracts from 1980 to 1990, we estimate a simultaneous system of regressions for tract population and employment growth. Six different weight matrices are tested, ranging from simple contiguity matrices to more complex matrices based on commute flows between census tracts. We also examine whether the inclusion of detailed information on land use improves performance of the lagged adjustment model. The results provide insights for future applications of econometric population-employment growth models. We found that the estimated lag parameters were consistent with dynamic stability for the models that included detailed land use data. Results varied for different weight matrices, but variation was mostly confined to interaction between population and employment growth. [source] Mixed-mode chromatography/isotope ratio mass spectrometry,RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 5 2010James S. O. McCullagh Liquid chromatography coupled to molecular mass spectrometry (LC/MS) has been a standard technique since the early 1970s but liquid chromatography coupled to high-precision isotope ratio mass spectrometry (LC/IRMS) has only been available commercially since 2004. This development has, for the first time, enabled natural abundance and low enrichment ,13C measurements to be applied to individual analytes in aqueous mixtures creating new opportunities for IRMS applications, particularly for the isotopic study of biological molecules. A growing number of applications have been published in a range of areas including amino acid metabolism, carbohydrates studies, quantification of cellular and plasma metabolites, dietary tracer and nucleic acid studies. There is strong potential to extend these to new compounds and complex matrices but several challenges face the development of LC/IRMS methods. To achieve accurate isotopic measurements, HPLC separations must provide baseline-resolution between analyte peaks; however, the design of current liquid interfaces places severe restrictions on compatible flow rates and in particular mobile phase compositions. These create a significant challenge on which reports associated with LC/IRMS have not previously focused. Accordingly, this paper will address aspects of chromatography in the context of LC/IRMS, in particular focusing on mixed-mode separations and their benefits in light of these restrictions. It aims to provide an overview of mixed-mode stationary phases and of ways to improve high aqueous separations through manipulation of parameters such as column length, temperature and mobile phase pH. The results of several practical experiments are given using proteogenic amino acids and nucleosides both of which are of noted importance in the LC/IRMS literature. This communication aims to demonstrate that mixed-mode stationary phases provide a flexible approach given the constraints of LC/IRMS interface design and acts as a practical guide for the development of new chromatographic methods compatible with LC/IRMS applications. Copyright © 2010 John Wiley & Sons, Ltd. [source] A reliable analytical approach based on gas chromatography coupled to triple quadrupole and time-of-flight mass analyzers for the determination and confirmation of polycyclic aromatic hydrocarbons in complex matrices from aquaculture activitiesRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 13 2009Jaime Nácher-Mestre The potential of gas chromatography coupled to tandem mass spectrometry (GC/MS/MS) with a triple quadrupole analyzer (QqQ) has been investigated for the quantification and reliable identification of sixteen polycyclic aromatic hydrocarbons (PAHs) from the EPA priority list in animal and vegetable samples from aquaculture activities, whose fat content ranged from 5 to 100%. Matrices analyzed included fish fillet, fish feed, fish oil and linseed oil. Combining optimized saponification and solid-phase extraction led to high efficiency in the elimination of interfering compounds, mainly fat, from the extracts. The developed procedure minimized the presence of these interfering compounds in the extracts and provided satisfactory recoveries of PAHs. The excellent sensitivity and selectivity of GC/(QqQ)MS/MS in selected reaction monitoring (SRM) allowed to reach limits of detection at pg/g levels. Two SRM transitions were acquired for each analyte to ensure reliable identification of compounds detected in samples. Confirmation of positive findings was performed by GC coupled to high-resolution time-of-flight mass spectrometry (GC/TOFMS). The accurate mass information provided by GC/TOFMS in full acquisition mode together with its high mass resolution makes it a powerful analytical tool for the unequivocal confirmation of PAHs in the matrices tested. The method developed was applied to the analysis of real-world samples of each matrix studied with the result of detecting and confirming the majority of analytes at the µg/kg level by both QqQ and TOF mass spectrometers. Copyright © 2009 John Wiley & Sons, Ltd. [source] Extracting metabolite ions out of a matrix background by combined mass defect, neutral loss and isotope filtrationRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 2 2009Filip Cuyckens Mass defect, neutral loss and isotope filtration techniques were applied to electrospray ionization mass spectrometry (ESI-MS) data obtained for in vivo and in vitro samples of drug metabolism studies. A combination of these post-acquisition processing techniques was shown to be more powerful than the use of one of these tools alone for the detection in complex matrices of metabolites of candidate drugs with a characteristic isotope pattern (e.g. containing bromine, chlorine, or a high proportion of radiolabeled drug (12C/14C)) or characteristic neutral losses. In combination with ,all-in-one' data acquisition this methodology is able to perform software-driven constant neutral loss scanning for an unlimited number of mass differences at any time after analysis. Highly selective MS chromatograms were obtained with excellent correlation with their corresponding radiochromatograms. Copyright © 2009 John Wiley & Sons, Ltd. [source] High-speed separation and characterization of major constituents in Radix Paeoniae Rubra by fast high-performance liquid chromatography coupled with diode-array detection and time-of-flight mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 1 2009E-Hu Liu A fast high-performance liquid chromatography (HPLC) method coupled with diode-array detection (DAD) and electrospray ionization time-of-flight mass spectrometry (ESI-TOFMS) has been developed for rapid separation and sensitive identification of major constituents in Radix Paeoniae Rubra (RPR). The total analysis time on a short column packed with 1.8-µm porous particles was about 20,min without a loss in resolution, six times faster than the performance of a conventional column analysis (115,min). The MS fragmentation behavior and structural characterization of major compounds in RPR were investigated here for the first time. The targets were rapidly screened from RPR matrix using a narrow mass window of 0.01,Da to restructure extracted ion chromatograms. Accurate mass measurements (less than 5,ppm error) for both the deprotonated molecule and characteristic fragment ions represent reliable identification criteria for these compounds in complex matrices with similar if not even better performance compared with tandem mass spectrometry. A total of 26 components were screened and identified in RPR including 11 monoterpene glycosides, 11 galloyl glucoses and 4 other phenolic compounds. From the point of time savings, resolving power, accurate mass measurement capability and full spectral sensitivity, the established fast HPLC/DAD/TOFMS method turns out to be a highly useful technique to identify constituents in complex herbal medicines. Copyright © 2008 John Wiley & Sons, Ltd. [source] Quantitative gas chromatography/time-of-flight mass spectrometry: a reviewBIOMEDICAL CHROMATOGRAPHY, Issue 7 2007Leah N. Williamson Abstract Time-of-flight (TOF) instruments have recently gained popularity in quantitative analyses. Normally, TOF mass spectrometers are used for accurate mass measurements for empirical formula verification. However, over the past decade, they have been used quantitatively as well. Because of the fast separations and narrow peaks that result from gas chromatography separations, scanning mass spectrometers are not ideal detectors. TOF mass spectrometers, however, have the ability to collect spectra at a faster rate. Two-dimensional gas chromatography has also been introduced to further resolve peaks from complex matrices. Two-dimensional gas chromatography results in a faster separation as well as narrower peaks. This paper reviews the methods currently in the literature for the quantitation of compounds using one- and two-dimensional gas chromatography and TOF mass spectrometry detection. Copyright © 2007 John Wiley & Sons, Ltd. [source] Determination of amino acids in rat vitreous perfusates by capillary electrophoresisELECTROPHORESIS, Issue 17 2004Kongthong Thongkhao-On Abstract In vivo determinations of amino acids are important for improving our understanding of physiological states of biological tissue function and dysfunction. However, the chemically complex matrix of different biological fluids complicates the assay of this important class of molecules. We introduce a method for characterizing the amino acid composition of submicroliter volumes of vitreous humor perfusates. Low-flow push-pull perfusion sampling is compatible with collecting small volume samples in a complicated matrix that are potentially difficult to separate. An efficient, sensitive, and rapid analysis of amino acids from in vivo perfusates of the vitreous is presented with 3-(4-carboxybenzoyl)-2-quinoline-carboxaldehyde (CBQCA) derivatitation and capillary electrophoresis (CE) separation with laser-induced fluorescence detection (LIF). Derivatization with CBQCA for up to 2 h provided high sensitivity and low detection limits at the nM level. Seventeen amino acids including D -serine (D -Ser) and D -aspartate (D -Asp) were resolved in less than 10 min. Importantly, D -Ser is separated from its enantiomeric pair. Characterization of vitreal amino acids with this assay technique will be useful for understanding ocular diseases and physiological mechanisms in vision. [source] Ultra-trace analysis of multiple endocrine-disrupting chemicals in municipal and bleached kraft mill effluents using gas chromatography,high-resolution mass spectrometryENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 2 2008Michael G. Ikonomou Abstract A comprehensive gas chromatographic,high-resolution mass spectrometric (GC-HRMS),based method was developed that permitted the simultaneous determination of 30 estrogenic endocrine-disrupting chemicals (EDCs) and related compounds, including surfactants, biogenic and synthetic steroids, fecal sterols, phytoestrogens, and plasticizers, in wastewater. Features of the method include low sample volume (,40 ml), optimized Florisil® cleanup to minimize matrix interferences and optimized analyte derivatization to improve sensitivity via GC-HRMS. Detection limits were in the low- to mid-ng/L range, and recoveries were greater than 60% for most target analytes. This new method allows for high throughput analysis of many organic wastewater contaminants in a complex matrix with relative standard deviation of less than 15% for most measurable compounds. The applicability of the method was demonstrated by examining wastewater samples from different origins. Compounds such as di(2-ethylhex-yl)phthalate, cholesterol, cholestanol, and other cholesterol derivatives were measured in much higher concentrations in untreated sewage and were reduced substantially in concentration by the treatment process. However, steroidal compounds, particularly estrone (E1), 17,-estradiol (E2), and estriol (E3), as well as plant sterols (except stigmastanol), were greater in the treated municipal wastewater versus the untreated effluent. Plant and fungi sterols, stigmastanol and ergosterol, were found largely associated with bleached kraft mill effluent (BKME) as compared to the municipal effluents. [source] Rethinking what constitutes suspended sedimentHYDROLOGICAL PROCESSES, Issue 9 2001Ian G. Droppo Abstract Although cohesive suspended sediment is now known to be transported primarily as flocculated material, there is still a misconception of what constitutes suspended sediment. Flocs represent a complex matrix of microbial communities, organic particles (e.g. detritus, extracellular polymers and cellular debris), inorganic particles (e.g. clays and silts) and substantial interfloc spaces (pores), which allow for the retention or flow through of water. Flocculation results in significant alteration of the hydrodynamics of the constituent particles (by modifying their effective size, shape, density and porosity), thereby affecting the transport of sediment and associated contaminants. The composition and structure of a floc is in a continuous state of change as the medium in which it is transported provides the floc with further building materials, energy, nutrients and chemicals for biological growth, chemical reactions and morphological development. As such, a floc's physical (e.g. transport), chemical (e.g. contaminant adsorption) and biological (community development and contaminant biotransformation) behaviour are also in a continuous state of change, with concomitant effects on their aquatic environment as a whole. Although it is recognized that floc form will influence floc behaviour, there is still a basic lack of knowledge of the complex links between the structural components of a floc and how their individual properties and behaviours in combination with others will influence a floc's physical, chemical and biological behaviour. This paper provides a comprehensive conceptual model that links the many interrelated structural components of typical flocs and their interrelated behavioural aspects, in order to enhance our understanding of what constitutes suspended sediment. Copyright © 2001 John Wiley & Sons, Ltd. [source] Caring in nursing: a different interpretationJOURNAL OF ADVANCED NURSING, Issue 6 2001Jane Sumner PhD MN RNC Caring in nursing: a different interpretation Aim.,To apply Habermas' (1995) Theory of Moral Consciousness and Communicative Action to the nurse,patient relationship, offering a different interpretation to the nurse,patient relationship that is caring in nursing. Rationale.,Many authors have described the nurse,patient relationship, but Habermas' theory synthesizes the components into a complex matrix that is caring in nursing. Findings.,The theory offers three claims to normative validity: the claim to truth which is the factual objective knowledge; the claim to truthfulness which refers to the intrasubjective self; and the claim to right which is the intersubjective interaction. The validity claims explain the patient's personal and illness self, the nurse's personal and professional self, and the interaction/discourse. The interaction is situation specific, and is identified as moral because dialogue/discourse requires a ,considerateness' of each for the other. ,Considerateness' in discourse requires certain rules, including that each participant has an equal voice, be followed in order for the Principle of Universalization to occur. Habermas draws on Kohlberg's (1981), and Selman's (1980) work to develop three levels of moral maturity of communication. These are preconventional, conventional, and postconventional. Initial moral maturity is egocentric, subjective, and obedient to authority. Maturity develops with recognition of other and reciprocity. At the postconventional level there is mutuality and the ability for abstract reasoning. There is a third person objectivity combining speaker and addressee/listener perspectives. Norms are not just accepted, they are reasoned through. This leads to justification of the norm, which is then accepted as valid. When the three validity claims are met and there is genuine ,considerateness' in the interaction there is communicative action. The reverse is strategic action, where the communication is coercive. When there is communicative action both patient and nurse are validated with a sense of fulfillment or Simultaneous characterization of isoflavonoids and astragalosides in two Astragalus species by high-performance liquid chromatography coupled with atmospheric pressure chemical ionization tandem mass spectrometryJOURNAL OF SEPARATION SCIENCE, JSS, Issue 13 2007Xi Zhang Abstract A method was developed for the simultaneous identification of astragalosides (AGs) and isoflavonoids (IFs) in the roots of Astragalus membranaceus and Astragalus mongholicus by HPLC coupled with atmospheric pressure chemical ionization MS/MS (HPLC-APCI-MS/MS). Diagnostic fragment ions of AGs and different group of IFs were obtained with one AG and eight IF standards analyzed by CID-MS, which were adopted as characteristic MS/MS fingerprints for further identification of these compounds in the two Astragalus species by using HPLC-APCI-MS/MS. A total of 20 IFs and 10 AGs were identified or tentatively identified. Among them, six IFs were detected in A. membranaceus for the first time and five IFs were firstly identified in A. mongholicus. The results indicate that HPLC-APCI-MS/MS is a powerful tool for the simultaneous characterization of IFs and AGs in complex matrix. [source] Analysis of flavor and perfume using an internally cooled coated fiber deviceJOURNAL OF SEPARATION SCIENCE, JSS, Issue 7 2007Yong Chen Abstract A miniaturized internally cooled coated fiber device was applied for the analysis of flavors and fragrances from various matrices. Its integration with a CTC CombiPAL autosampler enabled high throughput for the analysis of analytes in complex matrices that required simultaneous heating of the matrices and cooling of the fiber coating to achieve high extraction efficiency. It was found that up to ten times increase of extraction efficiencies was observed when the device was used to extract flavor compounds in water, even when limited sample temperatures were used to preserve the integrity of target compounds. The extraction of the flavor compounds in water with the device was reproducible, with RSD not larger than 15%. The lower limits of the linear ranges were in the low ppb range, which was about one order of magnitude smaller than those obtained with the commercialized 100 ,m PDMS fibers. Exhaustive extraction of some perfume ingredients from a complex matrix (shampoo) was realized. All achieved recoveries were not less than 80%. The repeatability of the extraction of the perfume compounds from shampoo was better than 10%. The linear ranges were about 1,3000 ,g/g, and the LOD was about 0.2,1 ,g/g. The automated internally cooled coated fiber device was demonstrated to be a powerful sample preparation tool in flavor and fragrance analysis. [source] Enrichment of peptides from plasma for peptidome analysis using multiwalled carbon nanotubesJOURNAL OF SEPARATION SCIENCE, JSS, Issue 6 2007Xin Li Abstract Human plasma contains a complex matrix of proteolytically derived peptides (plasma peptidome) that may provide a correlate of biological events occurring in the entire organism. Analyzing these peptides from a small amount of serum/plasma is difficult due to the complexity of the sample and the low levels of these peptides. Here, we describe a novel peptidome analysis approach using multiwalled carbon nanotubes (MWCNTs) as an alternative adsorbent to capture endogenous peptides from human plasma. Harvested peptides were analyzed by using liquid chromatography-mass spectrometry as a means of detecting and assessing the adsorbed molecules. The improved sensitivity and resolution obtained by using liquid chromatography-mass spectrometry allowed detection of 2521 peptide features (m/z 300,1800 range) in about 50 ,L of plasma. 374 unique peptides were identified with high confidence by two-dimensional liquid chromatography system coupled to a nano-spray ionization linear ion trap-mass spectrometer. High recovery of BSA digest peptides enriched with MWCNTs, in both standard buffer and high abundance protein solution, was observed. Comparative studies showed that MWCNTs were superior to C18 and C8 for the capture of the smaller peptides. This approach could hold promise of routine plasma peptidome analysis. [source]
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