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1

ANALYSIS OF TECHNICAL CHLORDANE BY GAS CHROMATOGRAPHY MASS SPECTROMETRY  

EPA Science Inventory

The composition of technical chlordane has been investigated by combined gas chromatography/mass spectrometry, employing a column commonly used for pesticide residue analysis. Partial or complete structure identification have been assigned to some 45 individual constituents. Many...

2

Differential Protein Expression Analysis via Liquid-Chromatography/Mass-Spectrometry Data Visualization  

E-print Network

Differential Protein Expression Analysis via Liquid-Chromatography/Mass-Spectrometry Data, Germany (a) (b) Figure 1: Interactive visualization of liquid-chromatography/mass-spectrometry data: (a of liquid-chromatography/mass-spectrometry data in a 3D space, which allows for the understanding

Linsen, Lars

3

ORGANIC WATER POLLUTANT ANALYSIS BY GAS CHROMATOGRAPHY-MASS SPECTROMETRY  

EPA Science Inventory

Gas chromatography-mass spectrometry is a widely used technique for the identification of organic chemicals in water. This paper describes the gas chromatograph-mass spectrometer system, the preparation and separation of samples, the selection of ionizing processes, the integrati...

4

Classification of natural resins by liquid chromatography-mass spectrometry and gas chromatography-mass spectrometry using chemometric analysis.  

PubMed

Twenty-six resins from six botanical sources belonging to the class Magnoliopsida were compared based on gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry data. The extracts were analysed by GC after silylation and by reversed phase LC combined with atmospheric pressure photoionisation (APPI) mass spectrometry. The chromatograms were re-organized in data matrices, where each sample was represented by a single column comprising 2755 observations (intensity, time, m/z) in GC-MS and 360 observations in LC-MS. A simple comparison of resin fingerprints was attempted by organizing data according to a three dimensional bubble chart (retention time against m/z where each point was a bubble which size represented the ion intensity) where it is possible to easily superimpose the fingerprints. Thus the common and different species can be easily observed enabling to classify the resins. Hierarchical cluster analysis based on characteristics of GC-MS and LC-MS profiles affords a complete description of the classes of the resins and shows that 26 resins are divided into five main clusters Commiphora mukul, Daniella oliveri, Gardenia gummifera, Canarium madagascariensis, Boswellia dalzielii and Boswellia serrata, respectively. In conclusion, the proposed method has been applied to three other resinous samples from the Burseraceae family to evaluate their alteration state. PMID:22885042

Rhourrhi-Frih, B; West, C; Pasquier, L; André, P; Chaimbault, P; Lafosse, M

2012-09-21

5

Targeted analysis of glycomics liquid chromatography/mass spectrometry data.  

PubMed

Hydrophilic interaction chromatography (HILIC) liquid chromatography/mass spectrometry (LC/MS) is appropriate for all native and reductively aminated glycan classes. HILIC carries the advantage that retention times vary predictably according to oligosaccharide composition. Chromatographic conditions are compatible with sensitive and reproducible glycomics analysis of large numbers of samples. The data are extremely useful for quantitative profiling of glycans expressed in biological tissues. With these analytical developments, the rate-limiting factor for widespread use of HILIC LC/MS in glycomics is the analysis of the data. In order to eliminate this problem, a Java-based open source software tool, Manatee, was developed for targeted analysis of HILIC LC/MS glycan datasets. This tool uses user-defined lists of compositions that specify the glycan chemical space in a given biological context. The program accepts high-resolution LC/MS data using the public mzXML format and is capable of processing a large data file in a few minutes on a standard desktop computer. The program allows mining of HILIC LC/MS data with an output compatible with multivariate statistical analysis. It is envisaged that the Manatee tool will complement more computationally intensive LC/MS processing tools based on deconvolution and deisotoping of LC/MS data. The capabilities of the tool were demonstrated using a set of HILIC LC/MS data on organ-specific heparan sulfates. PMID:20953780

Dreyfuss, Jonathan M; Jacobs, Christopher; Gindin, Yevgeniy; Benson, Gary; Staples, Gregory O; Zaia, Joseph

2011-01-01

6

AN EPA MANUAL FOR ORGANICS ANALYSIS USING GAS CHROMATOGRAPHY-MASS SPECTROMETRY  

EPA Science Inventory

This procedural manual defines the areas of applicability of gas chromatography-mass spectrometry in environmental analysis. The manual includes sample preparation methods specifically adapted to this measurement technique, data processing and interpretation methods, quality cont...

7

Proteomic Analysis of SARS Associated Coronavirus Using Two-Dimensional Liquid Chromatography Mass Spectrometry and  

E-print Network

in the analysis of other viruses. Keywords: coronavirus · proteome · mass spectrometry · glycosylationProteomic Analysis of SARS Associated Coronavirus Using Two-Dimensional Liquid Chromatography Mass Spectrometry and One-Dimensional Sodium Dodecyl Sulfate-Polyacrylamide Gel Electrophoresis Followed by Mass

Tian, Weidong

8

INTERLABORATORY COMPARISON OF THERMOSPRAY AND PARTICLE BEAM LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY INTERFACES: EVALUATION OF A CHLORINATED PHENOXY ACID HERBICIDE LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY ANALYSIS METHOD  

EPA Science Inventory

Seven laboratories participated in an interlaboratory evaluation of a liquid chromatography/mass spectrometry (LC/MS) method for the analysis of 10 chlorinated phenoxy acid herbicides. The focus of this evaluation was to test the intercomparability of LC/MS data obtained from two...

9

COMPARATIVE EVALUATION OF GC/MS (GAS CHROMATOGRAPHY/MASS SPECTROMETRY) DATA ANALYSIS PROCESSING  

EPA Science Inventory

Mass spectra obtained by fused silica capillary gas chromatography/mass spectrometry/data system (GC/MS/DS) analysis of mixtures of organic chemicals adsorbed on Tenax GC cartridges was subjected to manual and automated interpretative techniques. Synthetic mixtures (85 chemicals ...

10

ANALYSIS OF CHLORINATED HERBICIDES BY HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY  

EPA Science Inventory

A method that uses high performance liquid chromatography/mass spectrometry (HPLC/MS) for the analysis of chlorinated phenoxyacid herbicides is described. uring method development different techniques were used to increase both the sensitivity and the specificity of thermospray H...

11

Analysis of autoxidized fats by gas chromatography-mass spectrometry: III. Methyl linolenate  

Microsoft Academic Search

The gas chromatography-mass spectrometry (GC-MS) method developed in the preceding papers was extended to the analysis of\\u000a autoxidation products of methyl linolenate. Four isomeric hydroxy allylic trienes with a conjugated diene system were identified\\u000a after reduction of the linolenate hydroperoxides. All eight geometrictrans,cis- andtrans, trans-conjugated diene isomers of these hydroxy allylic compounds were identified and partially separated by GC of

E. N. Frankel; W. E. Neff; W. K. Rohwedder; B. P. S. Khambay; R. F. Garwood

1977-01-01

12

Gas chromatography-mass spectrometry methods for structural analysis of fatty acids  

Microsoft Academic Search

Procedures for structural analysis of fatty acids are reviewed. The emphasis is on methods that involve gas chromatography-mass\\u000a spectrometry and, in particular, the use of picolinyl ester and dimethyloxazoline derivatives. These should be considered\\u000a as complementing each other, not simply as alternatives. However, additional derivatization procedures can be of value, including\\u000a hydrogenation and deuteration, and preparation of dimethyl disulfide and

William W. Christie

1998-01-01

13

Search on ruggedness of fast gas chromatography–mass spectrometry in pesticide residues analysis  

Microsoft Academic Search

In this study, suitability of fast gas chromatography–mass spectrometry (GC–MS) on a narrow-bore column with a programmed temperature vaporizer for the analysis of pesticide residues in non-fatty food was evaluated. The main objectives were ruggedness and stability of chromatographic system with regards to co-extractives injected. The chromatographic matrix induced response enhancement was found to be strongly dependent on the concentration

Michal Kirchner; Eva Matisová; Robert Otrekal; Andrea Hercegová; Jaap de Zeeuw

2005-01-01

14

Analysis of volatile organic compounds in groundwater samples by gas chromatography-mass spectrometry  

SciTech Connect

The Savannah River Site contains approximately 1500 monitoring wells from which groundwater samples are collected. Many of these samples are sent off-site for various analyses, including the determination of trace volatile organic compounds (VOCs). This report describes accomplishments that have been made during the past year which will ultimately allow VOC analysis to be performed on-site using gas chromatography-mass spectrometry. Through the use of the on-site approach, it is expected that there will be a substantial cost savings. This approach will also provide split-sample analysis capability which can serve as a quality control measure for off-site analysis.

Bernhardt, J.

1995-08-23

15

Microwave-assisted derivatization procedures for gas chromatography\\/mass spectrometry analysis  

Microsoft Academic Search

In this review, published applications of microwave-assisted derivatization procedures for gas chromatography\\/mass spectrometry\\u000a (GC\\/MS) are summarized. Among the broad range of analytical techniques available, GC\\/MS is still the method of choice for\\u000a most high-throughput screening procedures in forensic\\/clinical toxicology, doping control and food and environmental analysis.\\u000a Despite the many advantages of the GC\\/MS method, time-consuming derivatization steps are often required

Sandra L. Söderholm; Markus Damm; C. Oliver Kappe

2010-01-01

16

Keto acid profiling analysis as ethoxime/tert-butyldimethylsilyl derivatives by gas chromatography-mass spectrometry.  

PubMed

Organic acids, including keto acids, are key intermediates of central pathways in cellular metabolism. In this study, a comprehensive and reliable method was developed and optimized for the simultaneous measurement of 17 keto acids in various biological samples. The keto acids were converted to solvent extractable forms by ethoximation followed by tert-butyldimethylsilylation for direct analysis by gas chromatography-mass spectrometry in selected ion monitoring mode. The proposed method was precise (0.05-8.3, % RSD) and accurate (-10.5 to 5.3, % RE) with low limit of detection (0.01-0.5ng/mL) and good linearity (r>0.995) in the range of 0.01-5.0?g/mL. This was suitable for profiling analysis of targeted keto acids in human plasma, urine and rat brain tissue. PMID:23270938

Nguyen, Duc-Toan; Lee, Gwang; Paik, Man-Jeong

2013-01-15

17

Headspace analysis of engine oil by gas chromatography/mass spectrometry.  

PubMed

This study establishes the rationale necessary for determining the time to change engine oil. This is based on identifying gaseous components in new and used automobile lubricants. Key compounds, so-called "signature", are separated and identified qualitatively by coupled gas chromatography/mass spectrometry. Volatile antioxidants at zero miles and fuel contaminants at low mileage are observed in the headspace of engine oil. Several oxidative degradation components have been positively identified in the used oil, which include the following: acetaldehyde, acetone, butanal, 2-propanol, acetic acid, 2-hexanol, benzoic acid, benzaldehyde, and 1-pentanol. This study strongly suggests that the status of lubricating oil can be determined by the analysis of the gas phase above the oil. Most importantly, it opens the possibility of performing conditional maintenance of the combustion engine based on information obtained from gas sensors. PMID:11305675

Levermore, D M; Josowicz, M; Rees, W S; Janata, J

2001-03-15

18

Multivariate analysis of progressive thermal desorption coupled gas chromatography-mass spectrometry.  

SciTech Connect

Thermal decomposition of poly dimethyl siloxane compounds, Sylgard{reg_sign} 184 and 186, were examined using thermal desorption coupled gas chromatography-mass spectrometry (TD/GC-MS) and multivariate analysis. This work describes a method of producing multiway data using a stepped thermal desorption. The technique involves sequentially heating a sample of the material of interest with subsequent analysis in a commercial GC/MS system. The decomposition chromatograms were analyzed using multivariate analysis tools including principal component analysis (PCA), factor rotation employing the varimax criterion, and multivariate curve resolution. The results of the analysis show seven components related to offgassing of various fractions of siloxanes that vary as a function of temperature. Thermal desorption coupled with gas chromatography-mass spectrometry (TD/GC-MS) is a powerful analytical technique for analyzing chemical mixtures. It has great potential in numerous analytic areas including materials analysis, sports medicine, in the detection of designer drugs; and biological research for metabolomics. Data analysis is complicated, far from automated and can result in high false positive or false negative rates. We have demonstrated a step-wise TD/GC-MS technique that removes more volatile compounds from a sample before extracting the less volatile compounds. This creates an additional dimension of separation before the GC column, while simultaneously generating three-way data. Sandia's proven multivariate analysis methods, when applied to these data, have several advantages over current commercial options. It also has demonstrated potential for success in finding and enabling identification of trace compounds. Several challenges remain, however, including understanding the sources of noise in the data, outlier detection, improving the data pretreatment and analysis methods, developing a software tool for ease of use by the chemist, and demonstrating our belief that this multivariate analysis will enable superior differentiation capabilities. In addition, noise and system artifacts challenge the analysis of GC-MS data collected on lower cost equipment, ubiquitous in commercial laboratories. This research has the potential to affect many areas of analytical chemistry including materials analysis, medical testing, and environmental surveillance. It could also provide a method to measure adsorption parameters for chemical interactions on various surfaces by measuring desorption as a function of temperature for mixtures. We have presented results of a novel method for examining offgas products of a common PDMS material. Our method involves utilizing a stepped TD/GC-MS data acquisition scheme that may be almost totally automated, coupled with multivariate analysis schemes. This method of data generation and analysis can be applied to a number of materials aging and thermal degradation studies.

Van Benthem, Mark Hilary; Mowry, Curtis Dale; Kotula, Paul Gabriel; Borek, Theodore Thaddeus, III

2010-09-01

19

DETERMINATION OF VOLATILE ORGANIC COMPOUNDS IN SOILS USING EQUILIBRIUM HEADSPACE ANALYSIS AND CAPILLARY COLUMN GAS CHROMATOGRAPHY/MASS SPECTROMETRY  

EPA Science Inventory

Existing methods for determination of volatile organic compounds (VOCs) in soil matrices using the purge and trap technique with gas chromatography/mass spectrometry (GC/MS) have several problems, which include preserving sample integrity from collection to analysis and efficient...

20

ANALYSIS OF TRACE-LEVEL ORGANIC COMBUSTION PROCESS EMISSIONS USING NOVEL MULTIDIMENSIONAL GAS CHROMATOGRAPHY-MASS SPECTROMETRY PROCEDURES  

EPA Science Inventory

The paper discusses the analysis of trace-level organic combustion process emissions using novel multidimensional gas chromatography-mass spectrometry (MDGC-MS) procedures. It outlines the application of the technique through the analyses of various incinerator effluent and produ...

21

Analysis of autoxidized fats by gas chromatography-mass spectrometry: I. Methyl oleate  

Microsoft Academic Search

A structural investigation of autoxidation products of methyl oleate was carried out by gas chromatography-mass spectrometry\\u000a (GC-MS) of trimethylsilyl (TMS) ether derivatives. GC-MS using computer plots of selected masses afforded structural assignments\\u000a of GC peaks due to incompletely resolved mixtures. This method provided evidence of epoxy and keto esters which are not completely\\u000a separated from the main components consisting of

E. N. Frankel; W. E. Neff; W. K. Rohwedder; B. P. S. Khambay; R. F. Garwood; B. C. L. Weedon

1977-01-01

22

Analysis of autoxidized fats by gas chromatography-mass spectrometry: II. Methyl linoleate  

Microsoft Academic Search

The gas chromatography-mass spectrometry (GC-MS) approach developed in the preceding paper was applied for qualitative and\\u000a quantitative investigations of autoxidation products of methyl linoleate. A GC-MS computer summation method was standardized\\u000a with synthetic 9- and 13-hydroxyoctadecanoate. Equal amounts of 9- and 13-hydroperoxides were found in all samples of linoleate\\u000a autoxidized at different temperatures and peroxide levels. The results are consistent

E. N. Frankel; W. E. Neff; W. K. Rohwedder; B. P. S. Khambay; R. F. Garwood; B. C. L. Weedon

1977-01-01

23

Gas chromatography–mass spectrometry associated global analysis of rice root exudates under aseptical conditions  

Microsoft Academic Search

Components of rice root exudates were surveyed by gas chromatography–mass spectrometry (GC-MS) and the effect of phosphate (P) starvation was investigated. Rice seedlings were aseptically grown in controlled environments under P-supplied (+P) or P-deficient (–P) conditions. Root exudates were collected from the culture solution 4 and 8?days after treatment (D4 and D8, respectively), which contain the first and second 4-day

Katsumasa Suzuki; Keiki Okazaki; Keitaro Tawaraya; Mitsuru Osaki; Takuro Shinano

2009-01-01

24

Analysis of aliphatic biopolymers using thermochemolysis with tetramethylammonium hydroxide (TMAH) and gas chromatography–mass spectrometry  

Microsoft Academic Search

Selected aliphatic biopolyesters (cutins, cuticles and a suberin) isolated from different plants have been analyzed using thermochemolysis with tetramethylammonium hydroxide (TMAH). This method consists of a high-temperature saponification\\/transesterification, and yields methyl esters of fatty acids and the methyl ethers of alcohols, which are subsequently analyzed by gas chromatography and gas chromatography–mass spectrometry. The main compounds produced from the analyzed samples

Jose C. del Río; Patrick G. Hatcher

1998-01-01

25

Headspace Analysis of Philippine Civet Coffee Beans Using Gas Chromatography-Mass Spectrometry and Electronic Nose  

NASA Astrophysics Data System (ADS)

Civet coffee, the most expensive and best coffee in the world, is an economically important export product of the Philippines. With a growing threat of food adulteration and counterfeiting, a need for quality authentication is essential to protect the integrity and strong market value of Philippine civet coffee. At present, there is no internationally accepted method of verifying whether a bean is an authentic civet coffee. This study presented a practical and promising approach to identify and establish the headspace qualitative profile of Philippine civet coffee using electronic nose (E-nose) and gas chromatography-mass spectrometry (GC-MS). E-nose analysis revealed that aroma characteristic is one of the most important quality indicators of civet coffee. The findings were supported by GC-MS analysis. Principal component analysis (PCA) exhibited a clearly separated civet coffees from their control beans. The chromatographic fingerprints indicated that civet coffees differed with their control beans in terms of composition and concentration of individual volatile constituents.

Ongo, E.; Sevilla, F.; Antonelli, A.; Sberveglieri, G.; Montevecchi, G.; Sberveglieri, V.; de Paola, E. L.; Concina, I.; Falasconi, M.

2011-11-01

26

Analysis of mutagens from cooked foods by directly combined liquid chromatography-mass spectrometry.  

PubMed Central

Directly combined high performance liquid chromatography-mass spectrometry (LC/MS) has been studied as a method of analysis of heterocyclic aromatic mutagens in cooked foods, in the parts per billion concentration range. Identification and semiquantitative estimation of mutagens is based on accurate measurement of chromatographic retention (k') and molecular weight-selective detection of mutagens, which are protonated during passage of the chromatographic eluant into a thermospray interface of a quadrupole mass spectrometer. Standard chromatographic retention (k') values in two reversed-phase systems and data from thermospray mass spectra from nine mutagens are reported. An isolation scheme employing CH3OH extraction, acid-base partition, cellulose-trisulfo-Cu-phthalocyanine adsorption, and normal-phase HPLC was used prior to LC/MS analysis. Initial applications have been demonstrated in the analysis of 2-amino-3-methylimidazo[4,5-f]quinoline (IQ) and 2-amino-3,4-dimethylimidazo[4,5-f]quinoline (MeIQ) in broiled salmon flesh. Levels measured were estimated to be in the range 0.2 to 0.4 microgram/kg IQ and 0.4 to 0.9 microgram/kg MeIQ. The method is judged to be generally applicable with minimal sample prefractionation to detection of mutagens at the parts per billion level in cooked foods. PMID:3757957

Edmonds, C G; Sethi, S K; Yamaizumi, Z; Kasai, H; Nishimura, S; McCloskey, J A

1986-01-01

27

In situ Analysis of Organic Compounds on Mars using Chemical Derivatization and Gas Chromatography Mass Spectrometry  

NASA Technical Reports Server (NTRS)

One of the core science objectives of NASA's 2009 Mars Science Laboratory (MSL) mission is to determine the past or present habitability of Mars. The search for key organic compounds relevant to terrestrial life will be an important part of that assessment. We have developed a protocol for the analysis of amino acids and carboxylic acids in Mars analogue materials using gas chromatography mass spectrometry (GCMS). As shown, a variety of carboxylic acids were readily identified in soil collected from the Atacama Desert in Chile at part-per-billion levels by GCMS after extraction and chemical derivatization using the reagent N,N-tert.-butyl (dimethylsilyl) trifluoroacetamide (MTBSTFA). Several derivatized amino acids including glycine and alanine were also detected by GCMS in the Atacama soil at lower concentrations (chromatogram not shown). Lacking derivatization capability, the Viking pyrolysis GCMS instruments could not have detected amino acids and carboxylic acids, since these non-volatile compounds require chemical transformation into volatile species that are stable in a GC column. We are currently optimizing the chemical extraction and derivatization technique for in situ GCMS analysis on Mars. Laboratory results of analyses of Atacama Desert samples and other Mars analogue materials using this protocol will be presented.

Glavin, D. P.; Buch, A.; Cabane, M.; Coll, P.; Navarro-Gonzalez, R.; Mahaffy, P. R.

2005-01-01

28

Comprehensive analysis of lipids in biological systems by liquid chromatography-mass spectrometry.  

PubMed

Liquid chromatography-mass spectrometry (LC-MS)-based lipidomics has been a subject of dramatic developments over the past decade. This review focuses on state of the art in LC-MS-based lipidomics, covering all the steps of global lipidomic profiling. On the basis of review of 185 original papers and application notes, we can conclude that typical LC-MS-based lipidomics methods involve: (1) extraction using chloroform/MeOH or MTBE/MeOH protocols, both with addition of internal standards covering each lipid class; (2) separation of lipids using short microbore columns with sub-2-?m or 2.6-2.8-?m (fused-core) particle size with C18 or C8 sorbent with analysis time <30 min; (3) electrospray ionization in positive- and negative-ion modes with full spectra acquisition using high-resolution MS with capability to MS/MS. Phospholipids (phosphatidylcholines, phosphatidylethanolamines, phosphatidylinositols, phosphatidylserines, phosphatidylglycerols) followed by sphingomyelins, di- and tri-acylglycerols, and ceramides were the most frequently targeted lipid species. PMID:25309011

Cajka, Tomas; Fiehn, Oliver

2014-10-01

29

Analysis of aliphatic biopolymers using thermochemolysis with tetramethylammonium hydroxide (TMAH) and gas chromatography- mass spectrometry  

Microsoft Academic Search

Abstract—Selected aliphatic biopolyesters (cutins, cuticles and a suberin) isolated from diÄerent plants have,been,analyzed,using thermochemolysis,with,tetramethylammonium,hydroxide,(TMAH). This method consists of a high-temperature saponification\\/transesterification, and yields methyl esters of fatty acids and the methyl ethers of alcohols, which are subsequently analyzed by gas chromatography and,gas chromatography?mass spectrometry. The main,compounds,produced,from,the analyzed samples correspond to the methyl derivatives of long-chain fatty acids, hydroxy fatty acids

PATRICK G. HATCHER

1998-01-01

30

Molecular analysis of intact preen waxes of Calidris canutus (Aves: Scolopacidae) by gas chromatography\\/mass spectrometry  

Microsoft Academic Search

The intact preen wax esters of the red knot Calidris canutus were studied with gas chromatography\\/mass spectrometry (GC\\/MS) and GC\\/MS\\/MS. In this latter technique, transitions from the\\u000a molecular ion to fragment ions representing the fatty acid moiety of the wax esters were measured, providing additional resolution\\u000a to the analysis of wax esters. The C21?C32 wax esters are composed of complex

Marlèn H. A. Dekker; Theunis Piersma; Jaap S. Sinninghe Damsté

2000-01-01

31

Linker-assisted immunoassay and liquid chromatography/mass spectrometry for the analysis of glyphosate  

USGS Publications Warehouse

A novel, sensitive, linker-assisted enzyme-linked immunosorbent assay (L'ELISA) was compared to on-line solidphase extraction (SPE) with high-performance liquid chromatography/mass spectrometry (HPLC/MS) for the analysis of glyphosate in surface water and groundwater samples. The L'ELISA used succinic anhydride to derivatize glyphosate, which mimics the epitotic attachment of glyphosate to horseradish peroxidase hapten. Thus, L'ELISA recognized the derivatized glyphosate more effectively (detection limit of 0.1 ??g/L) and with increased sensitivity (10-100 times) over conventional ELISA and showed the potential for other applications. The precision and accuracy of L'ELISA then was compared with on-line SPE/HPLC/MS, which detected glyphosate and its degradate derivatized with 9-fluorenylmethyl chloroformate using negative-ion electrospray (detection limit 0.1 ??g/L, relative standard deviation ??15%). Derivatization efficiency and matrix effects were minimized by adding an isotope-labeled glyphosate (2-13C15N). The accuracy of L'ELISA gave a false positive rate of 18% between 0.1 and 1.0 ??g/L and a false positive rate of only 1% above 1.0 ??g/L. The relative standard deviation was ??20%. The correlation of L'ELISA and HPLC/MS for 66 surface water and groundwater samples was 0.97 with a slope of 1.28, with many detections of glyphosate and its degradate in surface water but not in groundwater.

Lee, E.A.; Zimmerman, L.R.; Bhullar, B.S.; Thurman, E.M.

2002-01-01

32

Correlation between peak capacity and protein sequence coverage in proteomics analysis by liquid chromatography-mass spectrometry\\/mass spectrometry  

Microsoft Academic Search

Liquid chromatography-mass spectrometry\\/mass spectrometry (LC-MS\\/MS) allows the acquisition of a vast amount of analytical data in the aim of identifying peptides and proteins. Difficulties arise when attempting to identify proteins from the results of analyses of their peptide digests. We investigated possible quantitative correlations between the peak capacity achieved in chromatographic analyses and the protein sequence coverage. For this purpose,

Jacob N. Fairchild; Matthew J. Walworth; Krisztián Horváth; Georges Guiochon

2010-01-01

33

DIRECT ANALYSIS OF RAT BILE FOR ACETAMINOPHEN AND TWO OF ITS CONJUGATED METABOLITES VIA THERMOSPRAY LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY  

EPA Science Inventory

Bile from rats treated with acetaminophen was analyzed by direct injection onto a thermospray liquid chromatography/mass spectrometry system. Two conjugated metabolites of acetaminophen were separated by the high-pressure liquid chromatographic system and analyzed by mass spectro...

34

Analysis of hydroxy fatty acids as pentafluorobenzyl ester, trimethylsilyl ether derivatives by electron ionization gas chromatography\\/mass spectrometry  

Microsoft Academic Search

Electron ionization (EI) gas chromatography\\/mass spectrometry (GC\\/MS) analysis of pentafluorobenzyl ester-trimethyl sllyl\\u000a ether (PFB-TMS) derivatives of hydroxy-subshtuted fatty acids provides structural information comparable to that obtained\\u000a in analysis of methyl ester-trimethyl silyl ether (Me-TMS) derivatives. Use of this derivative eliminates the need to prepare\\u000a two separate derivatives, the PFB-TMS derivative for molecular weight determination by electron capture ionization (negative\\u000a ions)

Pat Wheelan; Joseph A. Zirrolli; Robert C. Murphy

1995-01-01

35

Analysis of L-serine-O-phosphate in cerebrospinal spinal fluid by derivatization-liquid chromatography/mass spectrometry.  

PubMed

L-serine-O-phosphate (L-SOP), the precursor of L-serine, is a potent agonist against the group III metabotropic glutamate receptors (mGluRs) and, thus, is of interest as a potential biomarker for monitoring modulation of neurotransmitter release. So far, no reports are available on the analysis of L-SOP in cerebrospinal fluid (CSF). Here a novel method is presented to determine L-SOP levels in CSF employing precolumn derivatization with (5-N-succinimidoxy-5-oxopentyl)triphenylphosphonium bromide (SPTPP) coupled to liquid chromatography/mass spectrometry (derivatization-LC/MS, d-LC/MS). PMID:24534252

McNaney, Colleen A; Benitex, Yulia; Luchetti, David; Labasi, Jeffrey M; Olah, Timothy V; Morgan, Daniel G; Drexler, Dieter M

2014-05-01

36

Gas chromatography/mass spectrometry analysis of Laurus nobilis essential oil composition of northern Cyprus.  

PubMed

The chemical composition of the essential oil isolated from the leaves of the Laurus nobilis plant (from the Northern Cyprus Mountains) by hydrodistillation was analyzed by gas chromatography-mass spectrometry. Of the 81 compounds representing 98.74% of total oil, monocyclic monoterpenes such as 1,8-cineole (58.59%), alpha-terpinyl acetate (8.82%), and terpinene-4-ol (4.25%) were the main components. Bicyclic monoterpenes such as alpha- and beta- pinene (3.39-3.25%) and sabinene (3.32%) were also identified. The acyclic monoterpenes linalool (0.19%) and myrcenol (0.10%) were present in smaller amounts, and so were the sesquiterpenes. o-Cymene (1.30%) and p-cymene (1.83%) were the main, while cumin aldehyde (0.24%), dimethylstyrene (0.08%), eugenol (0.16%), methyl eugenol (0.05%), and carvacrol (0.05%) were found as minor, aromatic compounds of laurel oil. PMID:18158847

Yalçin, Hasan; Anik, Mehtap; Sanda, Murat Aydin; Cakir, Ahmet

2007-12-01

37

Analysis of volatile compounds of Malaysian Tualang (Koompassia excelsa) honey using gas chromatography mass spectrometry.  

PubMed

The constituents of honey's volatile compounds depend on the nectar source and differ depending on the place of origin. To date, the volatile constituents of Tualang honey have never been investigated. The objective of this study was to analyze the volatile compounds in local Malaysian Tualang honey. A continuous extraction of Tualang honey using five organic solvents was carried out starting from non-polar to polar solvents and the extracted samples were analysed using gas chromatography-mass spectrometry (GC-MS). Overall, 35 volatile compounds were detected. Hydrocarbons constitute 58.5% of the composition of Tualang honey. Other classes of chemical compounds detected included acids, aldehydes, alcohols, ketones, terpenes, furans and a miscellaneous group. Methanol yielded the highest number of extracted compounds such as acids and 5-(Hydroxymethyl) furfural (HMF). This is the first study to describe the volatile compounds in Tualang honey. The use of a simple one tube, stepwise, non-thermal liquid-liquid extraction of honey is a advantageous as it prevents sample loss. Further research to test the clinical benefits of these volatile compounds is recommended. PMID:24146441

Nurul Syazana, M S; Gan, S H; Halim, A S; Shah, Nurul Syazana Mohamad; Gan, Siew Hua; Sukari, Halim Ahmad

2013-01-01

38

Trace analysis of environmental matrices by large-volume injection and liquid chromatography-mass spectrometry.  

PubMed

The time-honored convention of concentrating aqueous samples by solid-phase extraction (SPE) is being challenged by the increasingly widespread use of large-volume injection (LVI) liquid chromatography-mass spectrometry (LC-MS) for the determination of traces of polar organic contaminants in environmental samples. Although different LVI approaches have been proposed over the last 40 years, the simplest and most popular way of performing LVI is known as single-column LVI (SC-LVI), in which a large-volume of an aqueous sample is directly injected into an analytical column. For the purposes of this critical review, LVI is defined as an injected sample volume that is ?10% of the void volume of the analytical column. Compared with other techniques, SC-LVI is easier to set up, because it requires only small hardware modifications to existing autosamplers and, thus, it will be the main focus of this review. Although not new, SC-LVI is gaining acceptance and the approach is emerging as a technique that will render SPE nearly obsolete for many environmental applications. In this review, we discuss: the history and development of various forms of LVI; the critical factors that must be considered when creating and optimizing SC-LVI methods; and typical applications that demonstrate the range of environmental matrices to which LVI is applicable, for example drinking water, groundwater, and surface water including seawater and wastewater. Furthermore, we indicate direction and areas that must be addressed to fully delineate the limits of SC-LVI. PMID:21847530

Busetti, Francesco; Backe, Will J; Bendixen, Nina; Maier, Urs; Place, Benjamin; Giger, Walter; Field, Jennifer A

2012-01-01

39

Headspace single-drop microextraction gas chromatography mass spectrometry for the analysis of volatile compounds from herba asari.  

PubMed

A rapid headspace single-drop microextraction gas chromatography mass spectrometry (SDME-GC-MS) for the analysis of the volatile compounds in Herba Asari was developed in this study. The extraction solvent, extraction temperature and time, sample amount, and particle size were optimized. A mixed solvent of n-tridecane and butyl acetate (1?:?1) was finally used for the extraction with sample amount of 0.750?g and 100-mesh particle size at 70°C for 15?min. Under the determined conditions, the pound samples of Herba Asari were directly applied for the analysis. The result showed that SDME-GC-MS method was a simple, effective, and inexpensive way to measure the volatile compounds in Herba Asari and could be used for the analysis of volatile compounds in Chinese medicine. PMID:23607049

Wang, Guan-Jie; Tian, Li; Fan, Yu-Ming; Qi, Mei-Ling

2013-01-01

40

Headspace Single-Drop Microextraction Gas Chromatography Mass Spectrometry for the Analysis of Volatile Compounds from Herba Asari  

PubMed Central

A rapid headspace single-drop microextraction gas chromatography mass spectrometry (SDME-GC-MS) for the analysis of the volatile compounds in Herba Asari was developed in this study. The extraction solvent, extraction temperature and time, sample amount, and particle size were optimized. A mixed solvent of n-tridecane and butyl acetate (1?:?1) was finally used for the extraction with sample amount of 0.750?g and 100-mesh particle size at 70°C for 15?min. Under the determined conditions, the pound samples of Herba Asari were directly applied for the analysis. The result showed that SDME-GC–MS method was a simple, effective, and inexpensive way to measure the volatile compounds in Herba Asari and could be used for the analysis of volatile compounds in Chinese medicine. PMID:23607049

Wang, Guan-Jie; Tian, Li; Fan, Yu-Ming; Qi, Mei-Ling

2013-01-01

41

Development and validation of a liquid chromatography-mass spectrometry assay for hair analysis of methylphenidate.  

PubMed

Methylphenidate (MPH) is a phenethylamine derivative used in the treatment of childhood attention-deficit hyperactivity disorder. MPH is biotransformed in the body by the hydrolysis of the methyl ester linkage to its metabolite, ritalinic acid. Whereas both compounds are usually measured in plasma and urine, preliminary observations show that only the parent compound is present in hair from treated individuals. Since in children hair samples can be easily collected without the need for special skills and exposing a patient to discomfort, hair testing of MPH should be an alternative to check compliance in a wider time-window than if using blood. A procedure based on liquid chromatography-mass spectrometry (LC-MS) has been developed for the determination of MPH in hair of treated children. After addition of 3,4-methylenedioxypropylamphetamine as internal standard, hair samples were overnight digested with 0.1M HCl at 37 degrees C. Then, after pH adjustment to 6 using 1N NaOH, and 0.1M phosphate buffer, the analyte was extracted with Bond-Elut Certify columns. Chromatographic separation was achieved at ambient temperature using a reverse phase column and a mobile phase of 80% 10mM ammonium acetate-20% acetonitrile with a 20 min gradient program. The mass spectrometer was operated in positive electrospray ionization and selected ion monitoring acquisition mode. The method was validated in the range 0.15-50 ng MPH/mg hair, using 20mg hair per assay. At three concentrations spanning the linear dynamic range of the assay, mean recoveries ranged between 73.2 and 77.1%. First results show MPH hair concentration varying from 0.15 to 4.17 ng/mg hair, with decreasing drug concentration in distal hair segments, even in children treated with the same MPH dose during the period corresponding to different segments. This fact could be either attributed to sebum or sweat shunt with the most proximal hair segment or drug degradation by cosmetic treatments in more distal segments. PMID:17980530

Marchei, E; Muñoz, J A; García-Algar, O; Pellegrini, M; Vall, O; Zuccaro, P; Pichini, S

2008-03-21

42

Supersonic gas chromatography/mass spectrometry.  

PubMed

A new gas chromatography/mass spectrometry (GC/MS) system was designed and evaluated which we have named 'Supersonic GC/MS'. It is based on a modification of a commercially available GC/MS system to include a supersonic molecular beam (SMB) MS interface. In this system the standard electron ionization (EI) ion source was replaced with a fly-through EI ion source mounted in the path of the SMB. A hyperthermal surface ionization (HSI) ion source combined with a 90 degrees ion mirror (for the EI-produced ions) was also added, and placed inside the quadrupole mass analyzer in place of its original EI ion source. The 'Supersonic GC/MS' system requires 18 cm added bench space plus the addition of an air-cooled 60 L/s diffusion pump and a 537 L/min rotary pump. The system is user friendly since all the gas flow rates, heated zones, sampling and data analysis are performed the same way as the original system and are computer-controlled via the original software. Similar EI sensitivity was obtained as with the original system for hexachlorobenzene and octafluoronaphthalene, while improved EI detection limits were demonstrated for methyl stearate and eicosane due to the significant enhancement of their molecular ion abundances. A GC/MS detection limit of 500 ag for pyrene was demonstrated using HSI. Good supersonic expansion cooling was achieved with large alkanes, despite the use of a rotary pump at the nozzle chamber instead of a diffusion pump. High temperature GC/MS analysis was demonstrated for large polycyclic aromatic hydrocarbons (PAHs) including ovalene and decacyclene (ten rings). Library searches with EI mass spectra are demonstrated, and it is explained why the enhancement of the molecular ion actually improves the library search in most cases. The analysis of large phthalate esters is also described, and the improvement obtained is shown to originate from their enhanced molecular and high mass fragment ions. PMID:11344542

Amirav, A; Gordin, A; Tzanani, N

2001-01-01

43

Size exclusion chromatography/mass spectrometry applied to the analysis of polysaccharides.  

PubMed

A novel method for analysing polysaccharide materials is described which employs size-exclusion chromatography (SEC) followed by detection by on-line electrospray ionisation mass spectrometry (ESI-MS) and off-line matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS). It is demonstrated through SEC/ESI ion trap mass spectrometry that the formation of multiply charged oligomer ions, which bind up to five sodium cations, allows the rapid analysis of polysaccharide ions with molecular weights in excess of 9 kDa. MALDI spectra generated from fractionation of the effluent collected from the same SEC separation are shown to be in good agreement with the ESI spectra with respect to molecular weight distributions and types of ions generated. ESI and MALDI mass spectra of samples obtained from sequential graded ethanol precipitation and SEC fractionation of acid and enzymatically digested arabinoxylan polysaccharides show important structural differences between polysaccharide fragments. In addition, a comparison is made between the mass spectra of native and permethylated SEC-separated fragments of acid and enzymatically treated arabinogalactan. Linkage information of the permethylated arabinogalactan oligomers can be rapidly established through the use of on-line SEC/ESI-MS( n) experiments. PMID:11746893

Deery, M J; Stimson, E; Chappell, C G

2001-01-01

44

Derivatization and fragmentation pattern analysis of natural and synthetic steroids, as their trimethylsilyl (oxime) ether derivatives by gas chromatography mass spectrometry: Analysis of dissolved steroids in wastewater samples  

Microsoft Academic Search

This paper reports the extension of our multiresidue analysis (MA) procedure with 18 natural and synthetic steroids; permitting the identification and quantification, in total of 81 pollutants from one solution, by a single injection, as their trimethylsilyl (TMS)-oxime ether\\/ester derivatives, by gas chromatography–mass spectrometry (GC–MS), within 31min. As a novelty to the field, basic researches, such as fragmentation pattern analysis

N. Andrási; A. Helenkár; Gy. Záray; A. Vasanits; I. Molnár-Perl

2011-01-01

45

Targeted Chiral Analysis of Bioactive Arachidonic Acid Metabolites Using Liquid-Chromatography-Mass Spectrometry  

PubMed Central

A complex structurally diverse series of eicosanoids arises from the metabolism of arachidonic acid. The metabolic profile is further complicated by the enantioselectivity of eicosanoid formation and the variety of regioisomers that arise. In order to investigate the metabolism of arachidonic acid in vitro or in vivo, targeted methods are advantageous in order to distinguish between the complex isomeric mixtures that can arise by different metabolic pathways. Over the last several years this targeted approach has become more popular, although there are still relatively few examples where chiral targeted approaches have been employed to directly analyze complex enantiomeric mixtures. To efficiently conduct targeted eicosanoid analyses, LC separations are coupled with collision induced dissociation (CID) and tandem mass spectrometry (MS/MS). Product ion profiles are often diagnostic for particular regioisomers. The highest sensitivity that can be achieved involves the use of selected reaction monitoring/mass spectrometry (SRM/MS); whereas the highest specificity is obtained with an SRM transitions between an intense parent ion, which contains the intact molecule (M) and a structurally significant product ion. This review article provides an overview of arachidonic acid metabolism and targeted chiral methods that have been utilized for the analysis of the structurally diverse eicosanoids that arise. PMID:24957514

Mesaros, Clementina; Blair, Ian A.

2012-01-01

46

Comparative Analysis of Mass Spectral Similarity Measures on Peak Alignment for Comprehensive Two-Dimensional Gas Chromatography Mass Spectrometry  

PubMed Central

Peak alignment is a critical procedure in mass spectrometry-based biomarker discovery in metabolomics. One of peak alignment approaches to comprehensive two-dimensional gas chromatography mass spectrometry (GC×GC-MS) data is peak matching-based alignment. A key to the peak matching-based alignment is the calculation of mass spectral similarity scores. Various mass spectral similarity measures have been developed mainly for compound identification, but the effect of these spectral similarity measures on the performance of peak matching-based alignment still remains unknown. Therefore, we selected five mass spectral similarity measures, cosine correlation, Pearson's correlation, Spearman's correlation, partial correlation, and part correlation, and examined their effects on peak alignment using two sets of experimental GC×GC-MS data. The results show that the spectral similarity measure does not affect the alignment accuracy significantly in analysis of data from less complex samples, while the partial correlation performs much better than other spectral similarity measures when analyzing experimental data acquired from complex biological samples. PMID:24151524

2013-01-01

47

High Throughput Quantitative Analysis of Serum Proteins using Glycopeptide Capture and Liquid Chromatography Mass Spectrometry  

SciTech Connect

It is expected that the composition of the serum proteome can provide valuable information about the state of the human body in health and disease, and that this information can be extracted via quantitative proteomic measurements. Suitable proteomic techniques need to be sensitive, reproducible and robust to detect potential biomarkers below the level of highly expressed proteins, to generate data sets that are comparable between experiments and laboratories, and have high throughput to support statistical studies. In this paper, we report a method for high throughput quantitative analysis of serum proteins. It consists of the selective isolation of peptides that are N-linked glycosylated in the intact protein, the analysis of these, no de-glycosylated peptides by LC-ESI-MS, and the comparative analysis of the resulting patterns. By focusing selectively on a few formerly N-linked glycopeptides per serum protein, the complexity of the analyte sample is significantly reduced and the sensitivity and throughput of serum proteome analysis are increased compared with the analysis of total tryptic peptides from unfractionated samples. We provide data that document the performance of the method and show that sera from untreated normal mice and genetically identical mice with carcinogen induced skin cancer can be unambiguously discriminated using unsupervised clustering of the resulting peptide patterns. We further identify, by tandem mass spectrometry, some of the peptides that were consistently elevated in cancer mice compared to their control littermates.

Zhang, Hui; Yi, Eugene C.; Li, Xiao-jun; Mallick, Parag; Kelly-Spratt, Karen S.; Masselon, Christophe D.; Camp, David G.; Smith, Richard D.; Kemp, Christopher; Aebersold, Ruedi

2005-02-01

48

Analysis of macrolide antibiotics in river water by solid-phase extraction and liquid chromatography–mass spectrometry  

Microsoft Academic Search

A liquid chromatography–mass spectrometry (LC–MS) method was developed for the determination of five macrolides in natural water samples, using kitasamycin as surrogate. The macrolides were extracted from water samples using Oasis HLB cartridges. Pre-concentration factors up to 250 were obtained. Separation was carried out in an end-capped silica-based C18 column and mobile phases consisting of water\\/acetonitrile mixtures containing ammonium acetate.

Sònia Abuin; Rosa Codony; Ramon Compañó; Mercè Granados; Maria Dolors Prat

2006-01-01

49

Disaccharide analysis of glycosaminoglycan mixtures by ultra-high-performance liquid chromatography-mass spectrometry.  

PubMed

Glycosaminoglycans are a family of polysaccharides widely distributed in all eukaryotic cells. These polyanionic, linear chain polysaccharides are composed of repeating disaccharide units that are often differentially substituted with sulfo groups. The diversity of glycosaminoglycan structures in cells, tissues and among different organisms reflect their functional an evolutionary importance. Glycosaminoglycan composition and structure also changes in development, aging and in disease progression, making their accurate and reliable analysis a critical, albeit, challenging endeavor. Quantitative disaccharide compositional analysis is one of the primary ways to characterize glycosaminoglycan composition and structure and has a direct relationship with glycosaminoglycan biological functions. In this study, glycosaminoglycan disaccharides, prepared from heparan sulfate/heparin, chondroitin sulfate/dermatan sulfate and neutral hyaluronic acid using multiple polysaccharide lyases, were fluorescently labeled with 2-aminoacridone, fractionated into 17 well-resolved components by reverse-phase ultra-performance liquid chromatography, and analyzed by electrospray ionization mass spectrometry. This analysis was successfully applied to cell, tissue, and biological fluid samples for the picomole level detection of glycosaminoglycan composition and structure. PMID:22236563

Yang, Bo; Chang, Yuqing; Weyers, Amanda M; Sterner, Eric; Linhardt, Robert J

2012-02-17

50

High-throughput metabolic flux analysis based on gas chromatography-mass spectrometry derived 13C constraints.  

PubMed

13C-constrained flux balancing analysis based on gas chromatography-mass spectrometry data is presented here as a simple and robust method for the estimation of intracellular carbon fluxes. In this approach, the underdetermined system of metabolite balances deduced from stoichiometric relations and measured extracellular rates is complemented with 13C constraints from metabolic flux ratio analysis. Fluxes in central carbon metabolism of exponentially growing Escherichia coli were estimated by 13C-constrained flux balancing from three different 13C-labeled glucose experiments. The best resolution of the network was achieved using 13C constraints derived from [U-13C]glucose and [1-13C]glucose experiments. The corresponding flux estimate was in excellent agreement with a solution that was independently obtained with a comprehensive isotopomer model. This new methodology was also demonstrated to faithfully capture the intracellular flux distribution in E. coli shake flasks and 1-ml deep-well microtiter plates. Due to its simplicity, speed, and robustness, 13C-constrained metabolic flux balancing is promising for routine and high-throughput analysis on a miniaturized scale. PMID:14751266

Fischer, Eliane; Zamboni, Nicola; Sauer, Uwe

2004-02-15

51

Intratracheal gas analysis for volatile substances by gas chromatography/mass spectrometry--application to forensic autopsies.  

PubMed

Intratracheal gas analysis was carried out by gas chromatography/mass spectrometry (GC/MS) in 20 burned body cases (13 males and 7 females). Volatile aromatic and aliphatic hydrocarbons were detected by GC/MS using a GS-Q column with the intratracheal gas as well as the blood in 19 cases. The characteristic patterns of mass chromatograms for gasoline, kerosene (gas oil), and liquid petroleum gas could be differentiated from each other using the intratracheal gas. The burned body in one case showed no presence of volatile substances in the intratracheal gas, nor intratracheal soot, although high concentrations (1 microg/g and more) of volatile substances were detected on the clothes. The victim also had normal CO-Hb concentrations (0.1 to 0.2%) in the heart blood. The results of intratracheal gas analysis were consistent with signs of the vital reaction. In conclusion, intratracheal gas analysis provides a supportive method for diagnosing the cause of death in burned bodies, and yields for at least 48 hours valuable information on volatile hydrocarbons (being detected in deliberate or accidental fire cases) to which the body had been exposed just before death. PMID:11210932

Takayasu, T; Ohshima, T; Kondo, T; Sato, Y

2001-01-01

52

Targeted liquid chromatography–mass spectrometry analysis of serum acylcarnitines in acetaminophen toxicity in children  

PubMed Central

Aim Long-chain acylcarnitines have been postulated to be sensitive biomarkers of acetaminophen (APAP)-induced hepatotoxicity in mouse models. In the following study, the relationship of acylcarnitines with other known indicators of APAP toxicity was examined in children receiving low-dose (therapeutic) and high-dose (‘overdose’ or toxic ingestion) exposure to APAP. Materials & methods The study included three subject groups: group A (therapeutic dose, n = 187); group B (healthy controls, n = 23); and group C (overdose, n = 62). Demographic, clinical and laboratory data were collected for each subject. Serum samples were used for measurement of APAP protein adducts, a biomarker of the oxidative metabolism of APAP and for targeted metabolomics analysis of serum acylcarnitines using ultra performance liquid chromatography–triple-quadrupole mass spectrometry. Results Significant increases in oleoyl- and palmitoyl-carnitines were observed with APAP exposure (low dose and overdose) compared with controls. Significant increases in serum ALT, APAP protein adducts and acylcarnitines were observed in overdose children that received delayed treatment (time to treatment from overdose >24 h) with the antidote N-acetylcysteine. Time to peak APAP protein adducts in serum was shorter than that of the acylcarnitines and serum ALT. Conclusion Perturbations in long-chain acylcarnitines in children with APAP toxicity suggest that mitochrondrial injury and associated impairment in the ?-oxidation of fatty acids are clinically relevant as biomarkers of APAP toxicity. PMID:24521011

Bhattacharyya, Sudeepa; Yan, Ke; Pence, Lisa; Simpson, Pippa M; Gill, Pritmohinder; Letzig, Lynda G; Beger, Richard D; Sullivan, Janice E; Kearns, Gregory L; Reed, Michael D; Marshall, James D; Van Den Anker, John N; James, Laura P

2014-01-01

53

Systematic optimization of long gradient chromatography mass spectrometry for deep analysis of brain proteome.  

PubMed

The development of high-resolution liquid chromatography (LC) is essential for improving the sensitivity and throughput of mass spectrometry (MS)-based proteomics. Here we present systematic optimization of a long gradient LC-MS/MS platform to enhance protein identification from a complex mixture. The platform employed an in-house fabricated, reverse-phase long column (100 ?m × 150 cm, 5 ?m C18 beads) coupled to Q Exactive MS. The column was capable of achieving a peak capacity of ?700 in a 720 min gradient of 10-45% acetonitrile. The optimal loading level was ?6 ?g of peptides, although the column allowed loading as many as 20 ?g. Gas-phase fractionation of peptide ions further increased the number of peptide identification by ?10%. Moreover, the combination of basic pH LC prefractionation with the long gradient LC-MS/MS platform enabled the identification of 96?127 peptides and 10?544 proteins at 1% protein false discovery rate in a post-mortem brain sample of Alzheimer's disease. Because deep RNA sequencing of the same specimen suggested that ?16?000 genes were expressed, the current analysis covered more than 60% of the expressed proteome. Further improvement strategies of the LC/LC-MS/MS platform were also discussed. PMID:25455107

Wang, Hong; Yang, Yanling; Li, Yuxin; Bai, Bing; Wang, Xusheng; Tan, Haiyan; Liu, Tao; Beach, Thomas G; Peng, Junmin; Wu, Zhiping

2015-02-01

54

ANALYSIS OF SELECTED CHEMICAL GROUPS BY LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY  

EPA Science Inventory

The use of the moving-belt liquid chromatographic interface in combination with mass spectrometry was evaluated for determining detection limits of selected members of various chemical classes. mong the chemical classes examined were benzidines, nitrosoamines, anilines, nitroarom...

55

Different headspace solid phase microextraction--gas chromatography/mass spectrometry approaches to haloanisoles analysis in wine.  

PubMed

Three approaches in determination of six haloanisoles (2,4,6-trichloroanisole, 2,3,4-trichloroanisole, 2,3,6-trichloroanisole, tetrachloroanisole, pentachloroanisole and 2,4,6-tribromoanisole) in wine were compared. Comprehensive gas chromatography - time of flight mass spectrometry (GC×GC-ToF-MS) was described for the first time for this application and compared to gas chromatography-tandem mass spectrometry (GC-MS/MS) using triple quadrupole instrument. These techniques were compared with "standard" analytical approach using GC-MS(SIM). SPME method was developed and used for all separation methods (DVB/PDMS fiber, 70 °C, 30%NaCl, 20 min extraction). Extraction dependence on matrix was discussed using model wines with different ethanol contents (8%, 12%, and 18%) as well as water and different wines (dry white, dry red and sweet liqueur), with the lowest sensitivities obtained for highest ethanol contents in model wine and for liqueur wine. Limits of detection for GC×GC-ToF-MS method were 0.09-2.92 ng/L depending on the examined compound and matrix (compared to 0.1-13.3 ng/L obtained using GC/MS(SIM)). For GC-MS/MS method lower detection limits were achieved than for the GC×GC method (0.01-0.1 ng/L), however comprehensive gas chromatography-mass spectrometry provides full spectral information on analyzed compounds. Both methods had limits of detection far below odor thresholds of haloanisoles in wine, good linearity up to 2000 ng/L tested and good precision, what makes them suitable for analysis of these compounds in low ppt levels. PMID:23932370

Jele?, Henryk H; Dziadas, Mariusz; Majcher, Ma?gorzata

2013-10-25

56

Cellular lipid extraction for targeted stable isotope dilution liquid chromatography-mass spectrometry analysis.  

PubMed

The metabolism of fatty acids, such as arachidonic acid (AA) and linoleic acid (LA), results in the formation of oxidized bioactive lipids, including numerous stereoisomers(1,2). These metabolites can be formed from free or esterified fatty acids. Many of these oxidized metabolites have biological activity and have been implicated in various diseases including cardiovascular and neurodegenerative diseases, asthma, and cancer(3-7). Oxidized bioactive lipids can be formed enzymatically or by reactive oxygen species (ROS). Enzymes that metabolize fatty acids include cyclooxygenase (COX), lipoxygenase (LO), and cytochromes P450 (CYPs)(1,8). Enzymatic metabolism results in enantioselective formation whereas ROS oxidation results in the racemic formation of products. While this protocol focuses primarily on the analysis of AA- and some LA-derived bioactive metabolites; it could be easily applied to metabolites of other fatty acids. Bioactive lipids are extracted from cell lysate or media using liquid-liquid (l-l) extraction. At the beginning of the l-l extraction process, stable isotope internal standards are added to account for errors during sample preparation. Stable isotope dilution (SID) also accounts for any differences, such as ion suppression, that metabolites may experience during the mass spectrometry (MS) analysis(9). After the extraction, derivatization with an electron capture (EC) reagent, pentafluorylbenzyl bromide (PFB) is employed to increase detection sensitivity(10,11). Multiple reaction monitoring (MRM) is used to increase the selectivity of the MS analysis. Before MS analysis, lipids are separated using chiral normal phase high performance liquid chromatography (HPLC). The HPLC conditions are optimized to separate the enantiomers and various stereoisomers of the monitored lipids(12). This specific LC-MS method monitors prostaglandins (PGs), isoprostanes (isoPs), hydroxyeicosatetraenoic acids (HETEs), hydroxyoctadecadienoic acids (HODEs), oxoeicosatetraenoic acids (oxoETEs) and oxooctadecadienoic acids (oxoODEs); however, the HPLC and MS parameters can be optimized to include any fatty acid metabolites(13). Most of the currently available bioanalytical methods do not take into account the separate quantification of enantiomers. This is extremely important when trying to deduce whether or not the metabolites were formed enzymatically or by ROS. Additionally, the ratios of the enantiomers may provide evidence for a specific enzymatic pathway of formation. The use of SID allows for accurate quantification of metabolites and accounts for any sample loss during preparation as well as the differences experienced during ionization. Using the PFB electron capture reagent increases the sensitivity of detection by two orders of magnitude over conventional APCI methods. Overall, this method, SID-LC-EC-atmospheric pressure chemical ionization APCI-MRM/MS, is one of the most sensitive, selective, and accurate methods of quantification for bioactive lipids. PMID:22127066

Gelhaus, Stacy L; Mesaros, A Clementina; Blair, Ian A

2011-01-01

57

Acute toxicity of plant essential oils to scarab larvae (Coleoptera: Scarabaeidae) and their analysis by gas chromatography-mass spectrometry.  

PubMed

Larvae of scarab beetles (Coleoptera: Scarabaeidae) are important contaminant and root-herbivore pests of ornamental crops. To develop alternatives to conventional insecticides, 24 plant-based essential oils were tested for their acute toxicity against third instars of the Japanese beetle Popillia japonica Newman, European chafer Rhizotrogus majalis (Razoumowsky), oriental beetle Anomala orientalis (Waterhouse), and northern masked chafer Cyclocephala borealis Arrow. Diluted solutions were topically applied to the thorax, which allowed for calculating LD50 and LD90 values associated with 1 d after treatment. A wide range in acute toxicity was observed across all four scarab species. Of the 24 oils tested, allyl isothiocyanate, cinnamon leaf, clove, garlic, and red thyme oils exhibited toxicity to all four species. Allyl isothiocyanate was the most toxic oil tested against the European chafer, and among the most toxic against the Japanese beetle, oriental beetle, and northern masked chafer. Red thyme was also comparatively toxic to the Japanese beetle, oriental beetle, European chafer, and northern masked chafer. Interspecific variability in susceptibility to the essential oils was documented, with 12, 11, 8, and 6 of the 24 essential oils being toxic to the oriental beetle, Japanese beetle, European chafer, and northern masked chafer, respectively. Analysis of the active oils by gas chromatography-mass spectrometry revealed a diverse array of compounds, mostly consisting of mono- and sesquiterpenes. These results will aid in identifying active oils and their constituents for optimizing the development of plant essential oil mixtures for use against scarab larvae. PMID:23448028

Ranger, Christopher M; Reding, Michael E; Oliver, Jason B; Moyseenko, James J; Youssef, Nadeer; Krause, Charles R

2013-02-01

58

Practical aspects in gas chromatography-mass spectrometry for the analysis of pesticide residues in exotic fruits.  

PubMed

The most relevant parameters of a multimode inlet were optimized to increase the injection volume up to 25?L using solvent vent mode in order to improve the sensitivity of the gas chromatography-mass spectrometry system. Consequently, the implementation of a concurrent backflushing was necessary to largely prevent the expected loss of performance derived from such matrix load out of a general-purpose extraction (EN-15622-QuEChERS). Additionally, four mixtures of compounds used as analyte protectants were tested using spiked physalis to enhance the quality of signals. The chosen mixture remarkably improved sensitivity and yield better peak shapes, significantly more than others also tested. The analysis of pesticide residues in exotic fruits using instruments of limited selectivity is challenging since these complex matrices usually give notably dirty extracts. This scheme included an instrumental optimization and the addition of selected compounds that enabled to selectively reach limits of quantitation of 0.01mgkg(-1) for most analytes. PMID:25842302

España Amórtegui, Julio César; Guerrero Dallos, Jairo Arturo

2015-09-01

59

Gas chromatography-mass spectrometry analysis of different organic crude extracts from the local medicinal plant of Thymus vulgaris L  

PubMed Central

Objective To isolate and analyze the chemical composition in different crude extracts of from the leaves of locally grown of Thymus vulgaris L (T. vulgaris) by gas chromatography-mass spectrometry (GC-MS). Methods The shade dried leaves powder was extracted with methanol by using Soxhlet extractor. Methanol crude extracts of T. vulgaris and the derived fractions of hexane, chloroform, ethyl acetate and butanol were obtained. Results Qualitative analyses of various organic crude extracts of T. vulgaris by using GC-MS showed that there were different types of high and low molecular weight compounds. Most of the isolated and identified compounds by GC-MS in the crude extracts are basically biologically important. Further, the T. vulgaris leaf possessed certain characteristics that can be ascribed to cultivation on a domestic plantation. The crude extracts were prepared from the powder leaves of T. vulgaris for respective compounds can be chosen on the basis of above GC-MS analysis. Conclusions All the major compounds were identified and characterized by spectroscopic method in different organic crude extracts of T. vulgaris are biologically active molecules. Thus the identification of a good number of compounds in various crude extracts of T. vulgaris might have some ecological role. PMID:23570020

Hashmi, Laila Salim Al; Hossain, Mohammad Amzad; Weli, Afaf Mohammed; Al-Riyami, Qasim; Al-Sabahi, Jamal Nasser

2013-01-01

60

Chemical and technical challenges in the analysis of central carbon metabolites by liquid-chromatography mass spectrometry.  

PubMed

This review deals with chemical and technical challenges in the analysis of small-molecule metabolites involved in central carbon and energy metabolism via liquid-chromatography mass-spectrometry (LC-MS). The covered analytes belong to the prominent pathways in biochemical carbon oxidation such as glycolysis or the tricarboxylic acid cycle and, for the most part, share unfavorable properties such as a high polarity, chemical instability or metal-affinity. The topic is introduced by selected examples on successful applications of metabolomics in the clinic. In the core part of the paper, the structural features of important analyte classes such as nucleotides, coenzyme A thioesters or carboxylic acids are linked to "problematic hotspots" along the analytical chain (sample preparation and-storage, separation and detection). We discuss these hotspots from a chemical point of view, covering issues such as analyte degradation or interactions with metals and other matrix components. Based on this understanding we propose solutions wherever available. A major notion derived from these considerations is that comprehensive carbon metabolomics inevitably requires multiple, complementary analytical approaches covering different chemical classes of metabolites. PMID:24326023

Siegel, David; Permentier, Hjalmar; Reijngoud, Dirk-Jan; Bischoff, Rainer

2014-09-01

61

ANALYSIS OF TRIGLYCERIDES AND RELATED COMPOUNDS IN FOOD USING LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY TECHNIQUES  

Technology Transfer Automated Retrieval System (TEKTRAN)

The most common ionization sources available today to couple liquid chromatography (LC) with mass spectrometry (MS) are atmospheric pressure ionization (API) sources that form ions at ambient pressure and sample them into the high vacuum region of the mass analyzer. The two most popular API sources...

62

Analysis of chemical profiles of insect adhesion secretions by gas chromatography-mass spectrometry.  

PubMed

This article reports on the chemical analysis of molecular profiles of tarsal secretions of the desert locust Schistocerca gregaria (Forsskål, 1775) by gas chromatography hyphenated with quadrupol mass spectrometry (GC-MS) as well as (1)H-nuclear magnetic resonance ((1)H NMR) spectroscopy. Special focus of this study was to elaborate on sampling methods which enable selective microscale extraction of insect secretions in a spatially controlled manner, in particular tarsal adhesive secretions and secretions located on cuticle surfaces at the tibia. Various solvent sampling procedures and contact solid-phase microextraction (SPME) methods were compared in terms of comprehensiveness and extraction efficiencies as measured by signal intensities in GC-MS. Solvent sampling with water as extraction solvent gave access to the elucidation of chemical profiles of polar compound classes such as amino acids and carbohydrates, but is extremely tedious. Contact SPME on the other hand can be regarded as a simplified and more elegant alternative, in particular for the lipophilic compound fraction. Many proteinogenic amino acids and ornithine as well as carbohydrate monomers arabinose, xylose, glucose, and galactose were detected in tarsal secretions after acid hydrolysis of aqueous extracts. Qualitatively similar but quantitatively significantly different molecular profiles were found for the lipid fraction which contained mainly n-alkanes and internally branched monomethyl-, dimethyl-, and trimethyl-alkanes in the C23-C49 range as well as long chain fatty acids and aldehydes. Especially, hydrocarbons with >C40 carbon numbers have previously been rarely reported for insect secretions. The results suggest that the investigated insect secretions are complex emulsions which allow the attachment of tarsi on various otherwise incompatible materials of smooth and rough surfaces. The solid consistence of the established alkanes at ambient temperatures might contribute to a semi-solid consistence of the adhesive, amalgamating partly opposing functions such as slip resistance, tarsal release, desiccation resistance, and mechanical compliance. The methods developed can be extended to other similar applications of studying compositions of insect secretions of other species. PMID:25479867

Reitz, Manuela; Gerhardt, Heike; Schmitt, Christian; Betz, Oliver; Albert, Klaus; Lämmerhofer, Michael

2015-01-01

63

Analysis of Chlormequat residues in grain using liquid chromatography-mass spectrometry (LCMS\\/MS)  

Microsoft Academic Search

A fast, sensitive and specific method for routine determination of residues from Chlormequat (CAS no. 7003-89-6) is described.\\u000a The method is based on a simple clean-up using an SPE-C18 cartridge, high-performance liquid chromatography on a standard C18 column (Spherisorb S5 ODS1) and specific detection and quantification by electrospray mass spectrometry (LC-MS\\/MS). 13C-Chlormequat was synthesised for use as internal standard. Samples

Martin Vahl; Anette Graven; René K. Juhler

1998-01-01

64

ANALYSIS OF HAZARDOUS WASTE AND ENVIRONMENTAL EXTRACTS BY CAPILLARY GAS CHROMATOGRAPHY/FOURIER TRANSFORM INFRARED SPECTROMETRY AND CAPILLARY GAS CHROMATOGRAPHY/MASS SPECTROMETRY  

EPA Science Inventory

The relative sensitivities of fused-silica capillary column gas chromatography/Fourier transform infrared spectrometry (FSCC/GC/FT-IR) versus packed-column GC/FT-IR and FSCC/GC/FT-IR versus fused-silica capillary column gas chromatography/mass spectrometry (FSCC/GC/MS) were compa...

65

ANALYSIS OF HOUSTON AEROSOL SAMPLES BY GC/MS (GAS CHROMATOGRAPHY-MASS SPECTROMETRY) METHODS  

EPA Science Inventory

An analysis procedure developed to give a qualitative and quantitative analysis for organic compounds adsorbed on aerosols collected by Hi-Vol filters was adapted and applied to a similar analysis of aerosols collected by dichotomous filters. Analysis was conducted for five dicho...

66

Gas chromatography mass spectrometry computer analysis of volatile halogenated hydrocarbons in man and his environment--A multimedia environmental study.  

PubMed

As part of a study to make a comparative analysis of selected halogenated compounds in man and the environmental media, a quantitative gas chromatography mass spectrometric analysis of the levels of the halogenated compounds found in the breath, blood and urine of an exposed population (Old Love Canal area, Niagara, New York) and their immediate environment (air and water) was undertaken. In addition, levels of halogenated hydrocarbons in air samples taken in the general Buffalo, Niagara Falls area were determined. PMID:7448328

Barkley, J; Bunch, J; Bursey, J T; Castillo, N; Cooper, S D; Davis, J M; Erickson, M D; Harris, B S; Kirkpatrick, M; Michael, L C; Parks, S P; Pellizzari, E D; Ray, M; Smith, D; Tomer, K B; Wagner, R; Zweidinger, R A

1980-04-01

67

Development and Application of Pyrolysis Gas Chromatography/Mass Spectrometry for the Analysis of Bound Trinitrotoluene Residues in Soil  

USGS Publications Warehouse

TNT (trinitrotoluene) is a contaminant of global environmental significance, yet determining its environmental fate has posed longstanding challenges. To date, only differential extraction-based approaches have been able to determine the presence of covalently bound, reduced forms of TNT in field soils. Here, we employed thermal elution, pyrolysis, and gas chromatography/mass spectrometry (GC/MS) to distinguish between covalently bound and noncovalently bound reduced forms of TNT in soil. Model soil organic matter-based matrixes were used to develop an assay in which noncovalently bound (monomeric) aminodinitrotoluene (ADNT) and diaminonitrotoluene (DANT) were desorbed from the matrix and analyzed at a lower temperature than covalently bound forms of these same compounds. A thermal desorption technique, evolved gas analysis, was initially employed to differentiate between covalently bound and added 15N-labeled monomeric compounds. A refined thermal elution procedure, termed "double-shot analysis" (DSA), allowed a sample to be sequentially analyzed in two phases. In phase 1, all of an added 15N-labeled monomeric contaminant was eluted from the sample at relatively low temperature. In phase 2 during high-temperature pyrolysis, the remaining covalently bound contaminants were detected. DSA analysis of soil from the Louisiana Army Ammunition Plant (LAAP; ???5000 ppm TNT) revealed the presence of DANT, ADNT, and TNT. After scrutinizing the DSA data and comparing them to results from solvent-extracted and base/acid-hydrolyzed LAAP soil, we concluded that the TNT was a noncovalently bound "carryover" from phase 1. Thus, the pyrolysis-GC/MS technique successfully defined covalently bound pools of ADNT and DANT in the field soil sample.

Weiss, J.M.; Mckay, A.J.; Derito, C.; Watanabe, C.; Thorn, K.A.; Madsen, E.L.

2004-01-01

68

Analysis of furan in coffee of different provenance by head-space solid phase microextraction gas chromatography–mass spectrometry: effect of brewing procedures  

Microsoft Academic Search

A simple, sensitive and accurate method for the analysis of furan in roasted coffee has been used based on headspace–solid-phase micro-extraction (HS–SPME) coupled to gas chromatography–mass spectrometry (GC–MS). The extraction was performed using 75-µm carboxen\\/polydimethylsiloxane fiber. Ionic strength, extraction time and temperature, and desorption time were assessed as the most important parameters affecting the HS–SPME procedure and d4-furan was used

Lara La Pera; Alfredo Liberatore; Giuseppe Avellone; Serena Fanara; Giacomo Dugo; Pasquale Agozzino

2009-01-01

69

Derivatisation\\/solid-phase microextraction followed by gas chromatography–mass spectrometry for the analysis of phenoxy acid herbicides in aqueous samples  

Microsoft Academic Search

Different combinations of derivatisation and solid-phase microextraction followed by gas chromatography–mass spectrometry were optimised and evaluated for the analysis of phenoxy acid herbicides in water. The most successful derivatisation approach was aqueous-phase derivatisation with benzyl bromide. The benzyl esters were extracted most efficiently by the solid-phase microextraction fibre coated with polydimethylsiloxane–divinylbenzene. No carry-over problems were encountered with this fibre upon

Torben Nilsson; Daniela Baglio; Isabel Galdo-Miguez; Jørgen Øgaard Madsen; Sergio Facchetti

1998-01-01

70

Analysis of fatty acids in lung tissues using gas chromatography–mass spectrometry preceded by derivatization-solid-phase microextraction with a novel fiber  

Microsoft Academic Search

In this article, a laboratory-made sol–gel derived fiber with butyl methacrylate\\/hydroxy-terminated silicone oil (BMA\\/OH-TSO) coating was first used for headspace solid-phase microextraction (HS-SPME) of medium and long chain fatty acids after derivatization and applied to the analysis of fatty acids in lung tissues by coupling to gas chromatography–mass spectrometry (GC–MS). The experimental parameters for derivatization, HS-SPME and desorption were optimized.

Dongmei Cha; Mingming Liu; Zhaorui Zeng; Dong’e Cheng; Guoqing Zhan

2006-01-01

71

Analysis of alkali-lignin in a paper mill effluent decolourised with two Streptomyces strains by gas chromatography–mass spectrometry after cupric oxide degradation  

Microsoft Academic Search

Alkali-lignin samples obtained from an untreated paper mill effluent and from the effluent decolourised by the strains Streptomyces avermitilis CECT 3339 and Streptomyces scabies UAH 51 were analysed by gas chromatography–mass spectrometry (GC–MS) after cupric oxide degradation. The analysis of the depolymerisation products of the alkali-lignin from the decolourised effluents showed a strain specific modification of the aromatic moiety of

Manuel Hernández; Mar??a Jesús Hernández-Coronado; Maria Dolores Montiel; Juana Rodr??guez; Mar??a Enriqueta Arias

2001-01-01

72

Methods of analysis-Determination of pesticides in sediment using gas chromatography/mass spectrometry  

USGS Publications Warehouse

A method for the determination of 119 pesticides in environmental sediment samples is described. The method was developed by the U.S. Geological Survey (USGS) in support of the National Water Quality Assessment (NAWQA) Program. The pesticides included in this method were chosen through prior prioritization. Herbicides, insecticides, and fungicides along with degradates are included in this method and span a variety of chemical classes including, but not limited to, chloroacetanilides, organochlorines, organophosphates, pyrethroids, triazines, and triazoles. Sediment samples are extracted by using an accelerated solvent extraction system (ASE®, and the compounds of interest are separated from co-extracted matrix interferences (including sulfur) by passing the extracts through high performance liquid chromatography (HPLC) with gel-permeation chromatography (GPC) along with the use of either stacked graphitized carbon and alumina solid-phase extraction (SPE) cartridges or packed Florisil®. Chromatographic separation, detection, and quantification of the pesticides from the sediment-sample extracts are done by using gas chromatography with mass spectrometry (GC/MS). Recoveries in test sediment samples fortified at 10 micrograms per kilogram (?g/kg) dry weight ranged from 75 to 102 percent; relative standard deviations ranged from 3 to 13 percent. Method detection limits (MDLs), calculated by using U.S. Environmental Protection Agency procedures (40 CFR 136, Appendix B), ranged from 0.6 to 3.4 ?g/kg dry weight.

Hladik, Michelle L.; McWayne, Megan M.

2012-01-01

73

Analysis of anisoles in wines using pervaporation coupled to gas chromatography-mass spectrometry.  

PubMed

Two procedures for the determination of 2,4,6-trichloroanisole, 2,6-dichloroanisole and 2,4,6-tribromoanisole in tainted wines have been developed. Both methods are based on pervaporation (PV) of the analytes and final determination by gas chromatography-ion-trap tandem mass spectrometry (GC-MS). In the Approach A, pervaporation was directly coupled to the GC-MS system (PV-GC-MS/MS) and in Approach B a solid-phase cryogenic trap-thermal desorption (CT-TD) device was connected to the pervaporator (PV-CT-TD-GC-MS/MS). Results show that last coupling present better sensitivity as well as precision. Detection limits (DLs) for 2,4,6-trichloroanisole were estimated to be 25.8 and 4.2 ng l(-1) for Approaches A and B, respectively, when 10 ml of sample was analysed. Linear range of the calibration curves ranged from quantification limit to 15 ng for PV-GC-MS/MS and from quantification limit to 2 ng for PV-CT-TD-GC-MS/MS. Due to the low threshold odour concentration of these compounds in wine, Approach B is proposed as a reliable method for analytical quality control of this product. PMID:15499927

Gómez-Ariza, J L; García-Barrera, T; Lorenzo, F

2004-09-17

74

Characterization of human expired breath by solid phase microextraction and analysis using gas chromatography-mass spectrometry and differential mobility spectrometry  

E-print Network

Breath analysis has potential to become a new medical diagnostic modality. In this thesis, a method for the analysis of human expired breath was developed using gas chromatography-mass spectroscopy. It was subsequently ...

Merrick, William (William F. W.)

2005-01-01

75

PRECOLUMN SAMPLE ENRICHMENT DEVICE FOR ANALYSIS OF AMBIENT VOLATILE ORGANICS BY GAS CHROMATOGRAPHY-MASS SPECTROMETRY  

EPA Science Inventory

Gas chromatographic-mass spectrometric (GC/MS) identification of air pollutants generally requires a preconcentration step to provide sufficient sample for analysis. Cryogenic trapping is often used to enrich the sample since nitrogen and oxygen are not condensed. It does, howeve...

76

APPLICATION OF HIGH PERFORMANCE LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY TO ENVIRONMENTAL ANALYSIS  

EPA Science Inventory

High performance liquid chromatography (HPLC) coupled with nass spectronetry (MS) is described for the analysis of samples for environmental pollutants. uring the course of this work different techniques were used to increase both the sensitivity and specificity of HPLC/MS. hese ...

77

Accurate analysis of trace earthy-musty odorants in water by headspace solid phase microextraction gas chromatography-mass spectrometry.  

PubMed

A simple and sensitive method was developed for the simultaneous separation and determination of trace earthy-musty compounds including geosmin, 2-methylisoborneol, 2-isobutyl-3-methoxypyrazine, 2-isopropyl-3-methoxypyrazine, 2,3,4-trichloroanisole, 2,4,6-trichloroanisole, and 2,3,6-trichloroanisole in water samples. This method combined headspace solid-phase microextraction (HS-SPME) with gas chromatography-mass spectrometry and used naphthalene-d(8) as internal standard. A divinylbenzene/carboxen/polydimethylsiloxane fiber exposing at 90°C for 30 min provided effective sample enrichment in HS-SPME. These compounds were separated by a DB-1701MS capillary column and detected in selected ion monitoring mode within 12 min. The method showed a good linearity from 1 to 100 ng L(-1) and detection limits within (0.25-0.61 ng L(-1)) for all compounds. Using naphthalene-d(8) as the internal standard, the intra-day relative standard deviation (RSD) was within (2.6-3.4%), while the inter-day RSD was (3.5-4.9%). Good recoveries were obtained for tap water (80.5-90.6%), river water (81.5-92.4%), and lake water (83.5-95.2%) spiked at 10 ng L(-1). Compared with other methods using HS-SPME for determination of odor compounds in water samples, this present method had more analytes, better precision, and recovery. This method was successfully applied for analysis of earthy-musty odors in water samples from different sources. PMID:22740259

Ma, Kang; Zhang, Jin Na; Zhao, Min; He, Ya Juan

2012-06-01

78

Molecular analysis of intact preen waxes of Calidris canutus (Aves: Scolopacidae) by gas chromatography/mass spectrometry.  

PubMed

The intact preen wax esters of the red knot Calidris canutus were studied with gas chromatography/mass spectrometry (GC/MS) and GC/MS/MS. In this latter technique, transitions from the molecular ion to fragment ions representing the fatty acid moiety of the wax esters were measured, providing additional resolution to the analysis of wax esters. The C21-C32 wax esters are composed of complex mixtures of hundreds of individual isomers. The odd carbon-numbered wax esters are predominantly composed of even carbon-numbered n-alcohols (C14, C16, and C18) esterified predominantly with odd carbon-numbered 2-methyl fatty acids (C7, C9, C11, and C13), resulting in relatively simple distributions. The even carbon-numbered wax esters show a far more complex distribution due to a number of factors: (i) Their n-alcohol moieties are not dominated by even carbon-numbered n-alcohols esterified with odd carbon-numbered 2-methyl fatty acids, but odd and even carbon-numbered n-alcohols participate in approximately equal amounts; (ii) odd carbon-numbered methyl-branched alcohols participate abundantly in these wax ester clusters; and (iii) with increasing molecular weight, various isomers of the 2,6-, 2,8-, and 2,10-dimethyl branched fatty acids also participate in the even carbon-numbered wax esters. The data demonstrate that there is a clear biosynthetic control on the wax ester composition although the reasons for the complex chemistry of the waxes are not yet understood. PMID:10907788

Dekker, M H; Piersma, T; Damsté, J S

2000-05-01

79

Chemometric Analysis of Gas ChromatographyMass Spectrometry Data using Fast Retention Time Alignment via a Total Ion Current Shift Function  

SciTech Connect

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.

Nadeau, Jeremy S.; Wright, Bob W.; Synovec, Robert E.

2010-04-15

80

Response to weaning and dietary L-glutamine supplementation: metabolomic analysis in piglets by gas chromatography/mass spectrometry*  

PubMed Central

A novel metabolomic method based on gas chromatography/mass spectrometry (GC-MS) was applied to determine the metabolites in the serum of piglets in response to weaning and dietary L-glutamine (Gln) supplementation. Thirty-six 21-d-old piglets were randomly assigned into three groups. One group continued to suckle from the sows (suckling group), whereas the other two groups were weaned and their diets were supplemented with 1% (w/w) Gln or isonitrogenous L-alanine, respectively, representing Gln group or control group. Serum samples were collected to characterize metabolites after a 7-d treatment. Results showed that twenty metabolites were down-regulated significantly (P<0.05) in control piglets compared with suckling ones. These data demonstrated that early weaning causes a wide range of metabolic changes across arginine and proline metabolism, aminosugar and nucleotide metabolism, galactose metabolism, glycerophospholipid metabolism, biosynthesis of unsaturated fatty acid, and fatty acid metabolism. Dietary Gln supplementation increased the levels of creatinine,D-xylose, 2-hydroxybutyric acid, palmitelaidic acid, and ?-L-galactofuranose (P<0.05) in early weaned piglets, and were involved in the arginine and proline metabolism, carbohydrate metabolism, and fatty acid metabolism. A leave-one-out cross-validation of random forest analysis indicated that creatinine was the most important metabolite among the three groups. Notably, the concentration of creatinine in control piglets was decreased (P=0.00001) compared to the suckling piglets, and increased (P=0.0003) in Gln-supplemented piglets. A correlation network for weaned and suckling piglets revealed that early weaning changed the metabolic pathways, leading to the abnormality of carbohydrate metabolism, amino acid metabolism, and lipid metabolism, which could be partially improved by dietary Gln supplementation. These findings provide fresh insight into the complex metabolic changes in response to early weaning and dietary Gln supplementation in piglets. PMID:22761248

Xiao, Ying-ping; Wu, Tian-xing; Hong, Qi-hua; Sun, Jiang-ming; Chen, An-guo; Yang, Cai-mei; Li, Xiao-yan

2012-01-01

81

Response to weaning and dietary L-glutamine supplementation: metabolomic analysis in piglets by gas chromatography/mass spectrometry.  

PubMed

A novel metabolomic method based on gas chromatography/mass spectrometry (GC-MS) was applied to determine the metabolites in the serum of piglets in response to weaning and dietary L-glutamine (Gln) supplementation. Thirty-six 21-d-old piglets were randomly assigned into three groups. One group continued to suckle from the sows (suckling group), whereas the other two groups were weaned and their diets were supplemented with 1% (w/w) Gln or isonitrogenous L-alanine, respectively, representing Gln group or control group. Serum samples were collected to characterize metabolites after a 7-d treatment. Results showed that twenty metabolites were down-regulated significantly (P<0.05) in control piglets compared with suckling ones. These data demonstrated that early weaning causes a wide range of metabolic changes across arginine and proline metabolism, aminosugar and nucleotide metabolism, galactose metabolism, glycerophospholipid metabolism, biosynthesis of unsaturated fatty acid, and fatty acid metabolism. Dietary Gln supplementation increased the levels of creatinine, D-xylose, 2-hydroxybutyric acid, palmitelaidic acid, and ?-L-galactofuranose (P<0.05) in early weaned piglets, and were involved in the arginine and proline metabolism, carbohydrate metabolism, and fatty acid metabolism. A leave-one-out cross-validation of random forest analysis indicated that creatinine was the most important metabolite among the three groups. Notably, the concentration of creatinine in control piglets was decreased (P=0.00001) compared to the suckling piglets, and increased (P=0.0003) in Gln-supplemented piglets. A correlation network for weaned and suckling piglets revealed that early weaning changed the metabolic pathways, leading to the abnormality of carbohydrate metabolism, amino acid metabolism, and lipid metabolism, which could be partially improved by dietary Gln supplementation. These findings provide fresh insight into the complex metabolic changes in response to early weaning and dietary Gln supplementation in piglets. PMID:22761248

Xiao, Ying-ping; Wu, Tian-xing; Hong, Qi-hua; Sun, Jiang-ming; Chen, An-guo; Yang, Cai-mei; Li, Xiao-yan

2012-07-01

82

Combined liquid chromatography-mass spectrometry for trace analysis of pharmaceuticals  

NASA Astrophysics Data System (ADS)

A 252Cf-plasma desorption mass spectrometer (PDMS) for the analysis of thin layers from nonvolatile organic samples has been set up to be combined with a liquid chromatograph. A novel interface performs the direct inlet of the liquid sample through a capillary into the vacuum system of the spectrometer. Samples of drugs are periodically collected, transferred to the ion source and analysed using a rotating disk. This on-line sample preparation has been tested for three antiarrhythmic drugs using various solvents and mixtures.

Schmidt, Lothar; Danigel, Harald; Jungclas, Hartmut

1982-07-01

83

Carbon isotopic analysis of atmospheric methane by isotope-ratio-monitoring gas chromatography-mass spectrometry  

NASA Technical Reports Server (NTRS)

Less than 15 min are required for the determination of delta C(sub PDB)-13 with a precision of 0.2 ppt(1 sigma, single measurement) in 5-mL samples of air containing CH4 at natural levels (1.7 ppm). An analytical system including a sample-introduction unit incorporating a preparative gas chromatograph (GC) column for separation of CH4 from N2, O2, and Ar is described. The 15-min procedure includes time for operation of that system, high-resolution chromatographic separation of the CH4, on-line combustion and purification of the products, and isotopic calibration. Analyses of standards demonstrate that systematic errors are absent and that there is no dependence of observed values of delta on sample size. For samples containing 100 ppm or more CH4, preconcentration is not required and the analysis time is less than 5 min. The system utilizes a commercially available, high-sensitivity isotope-ratio mass spectrometer. For optimal conditions of smaple handling and combustion, performance of the system is within a factor of 2 of the shot-noise limit. The potential exists therefore for analysis of samples as small as 15 pmol CH4 with a standard deviation of less than 1 ppt.

Merritt, Dawn A.; Hayes, J. M.; Des Marais, David J.

1995-01-01

84

Analysis of pharmaceutical and other organic wastewater compounds in filtered and unfiltered water samples by gas chromatography/mass spectrometry  

USGS Publications Warehouse

Research on the effects of exposure of stream biota to complex mixtures of pharmaceuticals and other organic compounds associated with wastewater requires the development of additional analytical capabilities for these compounds in water samples. Two gas chromatography/mass spectrometry (GC/MS) analytical methods used at the U.S. Geological Survey National Water Quality Laboratory (NWQL) to analyze organic compounds associated with wastewater were adapted to include additional pharmaceutical and other organic compounds beginning in 2009. This report includes a description of method performance for 42 additional compounds for the filtered-water method (hereafter referred to as the filtered method) and 46 additional compounds for the unfiltered-water method (hereafter referred to as the unfiltered method). The method performance for the filtered method described in this report has been published for seven of these compounds; however, the addition of several other compounds to the filtered method and the addition of the compounds to the unfiltered method resulted in the need to document method performance for both of the modified methods. Most of these added compounds are pharmaceuticals or pharmaceutical degradates, although two nonpharmaceutical compounds are included in each method. The main pharmaceutical compound classes added to the two modified methods include muscle relaxants, opiates, analgesics, and sedatives. These types of compounds were added to the original filtered and unfiltered methods largely in response to the tentative identification of a wide range of pharmaceutical and other organic compounds in samples collected from wastewater-treatment plants. Filtered water samples are extracted by vacuum through disposable solid-phase cartridges that contain modified polystyrene-divinylbenzene resin. Unfiltered samples are extracted by using continuous liquid-liquid extraction with dichloromethane. The compounds of interest for filtered and unfiltered sample types were determined by use of the capillary-column gas chromatography/mass spectrometry. The performance of each method was assessed by using data on recoveries of compounds in fortified surface-water, wastewater, and reagent-water samples. These experiments (referred to as spike experiments) consist of fortifying (or spiking) samples with known amounts of target analytes. Surface-water-spike experiments were performed by using samples obtained from a stream in Colorado (unfiltered method) and a stream in New York (filtered method). Wastewater spike experiments for both the filtered and unfiltered methods were performed by using a treated wastewater obtained from a single wastewater treatment plant in New York. Surface water and wastewater spike experiments were fortified at both low and high concentrations and termed low- and high-level spikes, respectively. Reagent water spikes were assessed in three ways: (1) set spikes, (2) a low-concentration fortification experiment, and (3) a high-concentration fortification experiment. Set spike samples have been determined since 2009, and consist of analysis of fortified reagent water for target compounds included for each group of 10 to18 environmental samples analyzed at the NWQL. The low-concentration and high-concentration reagent spike experiments, by contrast, represent a one-time assessment of method performance. For each spike experiment, mean recoveries ranging from 60 to 130 percent indicate low bias, and relative standard deviations (RSDs) less than ( Of the compounds included in the filtered method, 21 had mean recoveries ranging from 63 to 129 percent for the low-level and high-level surface-water spikes, and had low ()132 percent]. For wastewater spikes, 24 of the compounds included in the filtered method had recoveries ranging from 61 to 130 percent for the low-level and high-level spikes. RSDs were 130 percent) or variable recoveries (RSDs >30 percent) for low-level wastewater spikes, or low recoveries ( Of the compounds included in the unfiltered method, 17 had mean spike recoveries ranging from 74

Zaugg, Steven D.; Phillips, Patrick J.; Smith, Steven G.

2014-01-01

85

Analysis of the thermal reaction products of para polyphenylene by combined gas chromatography-mass spectrometry  

NASA Technical Reports Server (NTRS)

Analysis of the volatiles and sublimate produced when para-polyphenylene is pyrolyzed to constant weight under vacuum in the temperature range from 380 to 1000 C indicates that the polymer undergoes thermal degradation in two stages. The first stage involved dehydrohalogenation, which is essentially a curing reaction that produces crosslinking between polyphenylene chains resulting from the loss of chlorine from the polymer in the form of hydrogen chloride. The second stage of the thermal degradation is dehydrogenation because hydrogen is the major volatile species. Increasing amounts of polycyclic aromatic hydrocarbons (phenanthrene and 9, 10 benzphenanthrene) in the sublimate, concomitant with increasing C/H ratios of the polymeric residue with pyrolysis temperature, is consistent with the buildup of polynuclear structures in the polymer matrix.

Fewell, L. L.

1976-01-01

86

Liquid chromatography-mass spectrometry analysis of diethylcarbamazine in human plasma for clinical pharmacokinetic studies.  

PubMed

A sensitive and selective liquid chromatographic method using mass spectrometric detection was developed for the determination of diethylcarbamazine (DEC) in human plasma. DEC and its stable isotope internal standard d3-DEC were extracted from 0.25mL of human plasma using solid phase extraction. Chromatography was performed using a Phenomenex Synergi 4? Fusion-RP column (2mm×250mm) with gradient elution. The retention time was approximately 4.8min. The assay was linear from 4 to 2200ng/mL. Analysis of quality control samples at 12, 300, and 1700ng/mL (N=15) had interday coefficients of variation of 8.4%, 5.4%, and 6.2%, respectively (N=15). Interday bias results were -2.2%, 6.0%, and 0.8%, respectively. Recovery of DEC from plasma ranged from 84.2% to 90.1%. The method was successfully applied to clinical samples from patients with lymphatic filariasis from a drug-drug interaction study between DEC and albendazole and/or ivermectin. PMID:24975211

Schmidt, Mark S; King, Christopher L; Thomsen, Edward K; Siba, Peter M; Sanuku, Nelly; Fleckenstein, Lawrence

2014-09-01

87

Gas Chromatography-Mass Spectrometry Experiment  

NSDL National Science Digital Library

Gas Chromotography-Mass Spectrometry (GC-MS) is an analysis used in many laboratory testing situations. This laboratory exercise explains this method and uses this method to analyse DMSO. This exercise includes images and screenshots, as well as group discussion questions and questions for individual exploration of mass spectrometry online. Users may download this experiment in Microsoft Word doc file format.

Solow, Mike

88

Complementary fragmentation pattern analysis by gas chromatography–mass spectrometry and liquid chromatography tandem mass spectrometry confirmed the precious lignan content of Cirsium weeds  

Microsoft Academic Search

In this paper, as novelties to the field, it is confirmed at first, that the fruits of Cirsium species, regarded as injurious weeds, do contain lignans, two, different butyrolactone-type glycoside\\/aglycone pairs: the well known arctiin\\/arctigenin and the particularly rare tracheloside\\/trachelogenin species. These experiences were supported by gas chromatography–mass spectrometry (GC–MS), by liquid chromatography tandem mass spectrometry (LC–MS\\/(MS)) and by nuclear

I. Boldizsár; M. Kraszni; F. Tóth; B. Noszál; I. Molnár-Perl

2010-01-01

89

Analysis of deteriorated rubber-based pressure sensitive adhesive by pyrolysis-gas chromatography\\/mass spectrometry and attenuated total reflectance Fourier transform infrared spectrometry  

Microsoft Academic Search

Rubber-based pressure sensitive adhesives of three packing tapes were exposed to sunlight for 6 months to accelerate the oxidation of the adhesives. The exposed adhesives and the unexposed adhesives were analyzed by attenuated total reflectance Fourier transform infrared spectrometry (ATR\\/FT-IR) and pyrolysis-gas chromatography\\/mass spectrometry (Py-GC\\/MS). The ATR\\/FT-IR spectra and the pyrograms changed drastically after the exposure. The pyrolyzate peaks of

Y. Kumooka

2006-01-01

90

Analysis of polyphenolic antioxidants from the fruits of three pouteria species by selected ion monitoring liquid chromatography-mass spectrometry.  

PubMed

Pouteria campechiana, Pouteria sapota, and Pouteria viridis are tropical plants in the Sapotaceae family that bear edible fruits. The fresh fruits of these three Pouteria species were each extracted, and activity-guided fractionations were performed to identify the antioxidant constituents. Seven polyphenolic antioxidants, gallic acid (1), (+)-gallocatechin (2), (+)-catechin (3), (-)-epicatechin (4), dihydromyricetin (5), (+)-catechin-3-O-gallate (6), and myricitrin (7), were isolated and identified. Extracts of the three Pouteria fruits were analyzed by a selected ion monitoring liquid chromatography-mass spectrometry method to quantify their polyphenolic antioxidants. The highest level of the seven measured polyphenols was found in P. sapota, the second highest in P. viridis, and the lowest in P. campechiana. The levels of the seven polyphenols corresponded with the results of the 1,1-diphenyl-2-picrylhydrazyl assay, by which P. sapota had the highest antioxidant activity, P. viridis the second highest, and P. campechiana the lowest. PMID:15366835

Ma, Jun; Yang, Hui; Basile, Margaret J; Kennelly, Edward J

2004-09-22

91

Analysis of almitrine and its metabolites in plasma using on-line fast atom bombardment liquid chromatography/mass spectrometry.  

PubMed

To validate a recently developed liquid chromatography/ultraviolet (LC/UV) method in a pharmacokinetic study of Vectarion (almitrine) where the unchanged drug, its five metabolites and an internal standard are analysed, on-line fast atom bombardment liquid chromatography/mass spectrometry (FAB LC/MS) with a moving belt interface has been used. Since the liquid chromatographic conditions required the use of perchloric acid FAB was chosen as ionization mode for the involatile perchlorates formed in the liquid chromatographic process. The use of FAB LC/MS allows the detection of the protonated molecular ions of all the components in the mixture. Furthermore, all the compounds show an intense peak at m/z 203, presenting a liquid chromatographic profile which is very similar to the profile obtained with UV detection. PMID:2907411

Luijten, W; Damien, G; Marchand, B; Capart, J

1988-10-01

92

Chemical Composition of Latent Fingerprints by Gas Chromatography-Mass Spectrometry  

ERIC Educational Resources Information Center

An experiment in which gas chromatography-mass spectrometry (GC-MS) is used for latent fingerprint extraction and analysis on glass beads or glass slides is conducted. The results determine that the fingerprint residues are gender dependent.

Hartzell-Baguley, Brittany; Hipp, Rachael E.; Morgan, Neal R.; Morgan, Stephen L.

2007-01-01

93

Quantification of Protein Phosphorylation by Liquid Chromatography-Mass Spectrometry  

E-print Network

Quantification of Protein Phosphorylation by Liquid Chromatography-Mass Spectrometry Michael J and quantification of specific phospho- rylation sites within a protein by mass spectrometry has proved challenging ionization liquid chroma- tography-mass spectrometry by quantifying phosphory- lation of troponin I

Vigoreaux, Jim O.

94

Quantitative Analysis of Tetramethylenedisulfotetramine ("Tetramine") Spiked into Beverages by Liquid Chromatography Tandem Mass Spectrometry with Validation by Gas Chromatography Mass Spectrometry  

SciTech Connect

Tetramethylenedisulfotetramine, commonly known as tetramine, is a highly neurotoxic rodenticide (human oral LD{sub 50} = 0.1 mg/kg) used in hundreds of deliberate food poisoning events in China. Here we describe a method for quantitation of tetramine spiked into beverages, including milk, juice, tea, cola, and water and cleaned up by C8 solid phase extraction and liquid-liquid extraction. Quantitation by high performance liquid chromatography tandem mass spectrometry (LC/MS/MS) was based upon fragmentation of m/z 347 to m/z 268. The method was validated by gas chromatography mass spectrometry (GC/MS) operated in SIM mode for ions m/z 212, 240, and 360. The limit of quantitation was 0.10 {micro}g/mL by LC/MS/MS versus 0.15 {micro}g/mL for GC/MS. Fortifications of the beverages at 2.5 {micro}g/mL and 0.25 {micro}g/mL were recovered ranging from 73-128% by liquid-liquid extraction for GC/MS analysis, 13-96% by SPE and 10-101% by liquid-liquid extraction for LC/MS/MS analysis.

Owens, J; Hok, S; Alcaraz, A; Koester, C

2008-11-13

95

Studies on the metabolism and the toxicological analysis of the nootropic drug fipexide in rat urine using gas chromatography–mass spectrometry  

Microsoft Academic Search

Qualitative studies are described on the metabolism and the toxicological analysis of the nootropic fipexide (FIP) in rat urine using gas chromatography–mass spectrometry (GC–MS). FIP was extensively metabolized to 1-(3,4-methylenedioxybenzyl)piperazine (MDBP), 4-chlorophenoxyacetic acid, 1-[2-(4-chlorophenoxy)acetyl]piperazine, N-(4-hydroxy-3-methoxy-benzyl)piperazine, piperazine, N-(3,4-methylenedioxybenzyl)ethylenediamine, and N-[2-(4-chlorophenoxy)acetyl]ethylenediamine. The authors’ systematic toxicological analysis (STA) procedure using full-scan GC–MS after acid hydrolysis of one urine aliquot, liquid-liquid extraction and acetylation

Roland F. Staack; Hans H. Maurer

2004-01-01

96

Rapid analysis of tile industry gaseous emissions by ion mobility spectrometry and comparison with solid phase micro-extraction/gas chromatography/mass spectrometry.  

PubMed

The present paper reports on a rapid method for the analysis of gaseous emissions from ceramic industry, based on ion mobility spectrometry (IMS) as a means for on-site monitoring of volatile organic compounds (VOCs) produced during tile baking. IMS was calibrated with a set of reference compounds (i.e. ethyl acetate, ethanol, ethylene glycol, diethylene glycol, acetaldehyde, formaldehyde, 2-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 1,3-dioxolane, 1,4-dioxane, benzene, toluene, cyclohexane, acetone, acetic acid) via air-flow permeation. The technique was tested on a laboratory-scale kiln and tiles prepared with selected glycol- and resin-based additives. Finally, the analytical method was applied to emissions from two industries in the Modena (Italy) ceramic area. The results of all experimental phases were compared to those obtained by solid phase micro-extraction/gas chromatography/mass spectrometry (SPME/GC/MS). IMS showed potential as a real-time monitoring device for quality assessment in ceramic industry emissions. IMS spectra, SPME/GC/MS data, relationship between additives/baking conditions and produced VOCs and advantages and limitations of both techniques will be discussed. PMID:17133278

Pozzi, R; Bocchini, P; Pinelli, F; Galletti, G C

2006-12-01

97

Quantitative solid phase microextraction--gas chromatography mass spectrometry analysis of five megastigmatrienone isomers in aged wine.  

PubMed

Megastigmatrienone is a key flavor compound in tobacco. It has also been detected in wine, where it may contribute to a tobacco/incense aroma, but its importance and concentration in wines had never previously been evaluated. A method was developed and validated for quantifying the five megastigmatrienone isomers in red and white wines. Megastigmatrienone isomers were extracted by headspace solid-phase microextraction (HS-SPME), with a 65 ?m film thickness polydimethylsiloxane-divinylbenzene (PDMS-DVB) fiber and analyzed using gas chromatography-mass spectrometry (GC/MS) in selected ion monitoring mode (SIM). Several parameters affecting the length of the adsorption process (i.e., adding salt, extraction time and extraction temperature) were tested. The optimum analytical conditions were established. The LOQ were between 0.06 ?g L(-1) and 0.49 ?g L(-1) for white wine and 0.11 ?g L(-1) and 0.98 ?g L(-1) for red wine, repeatability in both types of wine was less than 10% and recovery ranged from 96% for white wine to 94% for red wine. The five isomers of megastigmatrienone were quantified in red and white wines for the first time. Concentrations ranged from 2 ?g L(-1) to 41 ?g L(-1) in both red and white wines. Initial results revealed a link between wine aging and megastigmatrienone levels, indicating that megastigmatrienone may be a component in wine "bouquet". PMID:24528661

Slaghenaufi, Davide; Perello, Marie-Claire; Marchand-Marion, Stéphanie; Tempere, Sophie; de Revel, Gilles

2014-02-27

98

Direct analysis of intact glycidyl fatty acid esters in edible oils using gas chromatography-mass spectrometry.  

PubMed

Glycidyl esters (GE), fatty acid esters of glycidol, are process contaminants formed during edible oil processing. A novel direct method for the determination of intact GE in oils and fats based on gas chromatography-mass spectrometry (GC-MS) is presented. The method consists of a simple extraction step of GE from the lipid matrix, purification of the extract and isolation of GE by normal phase liquid chromatography (NPLC). Individual GE in the final fraction are separated and quantified by standard GC-MS operated in selected ion monitoring (SIM) mode. The setup and conditions of the GC-MS were optimized in such a way that thermal degradation of GE and artifact formation were prevented. The method exhibits very good performance parameters: the limit of detection was approximately 0.01 mg/kg for the individual GE (corresponding to 0.002-0.003 mg/kg of free glycidol), the repeatability was in the range of 5-12% for individual GE at levels above 0.1mg/kg, and recovery values ranged from 85 to 115% depending on the level and the chain identity of the GE. The comparison of experimental values with spiked levels and with the results obtained by other methods confirmed a good trueness. Over a period of several months of extensive use the method was found to be very reliable and rugged. PMID:23891377

Steenbergen, Herrald; Hrn?i?ík, Karel; Ermacora, Alessia; de Koning, Sjaak; Janssen, Hans-Gerd

2013-10-25

99

Complementary fragmentation pattern analysis by gas chromatography-mass spectrometry and liquid chromatography tandem mass spectrometry confirmed the precious lignan content of Cirsium weeds.  

PubMed

In this paper, as novelties to the field, it is confirmed at first, that the fruits of Cirsium species, regarded as injurious weeds, do contain lignans, two, different butyrolactone-type glycoside/aglycone pairs: the well known arctiin/arctigenin and the particularly rare tracheloside/trachelogenin species. These experiences were supported by gas chromatography-mass spectrometry (GC-MS), by liquid chromatography tandem mass spectrometry (LC-MS/(MS)) and by nuclear magnetic resonance (NMR) spectroscopy. The study reflects the powerful impact of the complementary chromatographic mass fragmentation evidences resulting in the identification and quantification, the extremely rare, with on line technique not yet identified and described, tracheloside/trachelogenin pair lignans, without authentic standard compounds. Fragmentation pattern analysis of the trimethylsilyl (TMS) derivative of trachelogenin, based on GC-MS, via two different fragmentation pathways confirmed the detailed structure of the trachelogenin molecule. The complementary chromatographic evidences have been unambiguously confirmed, by (1)H and (13)C NMR analysis of trachelogenin, isolated by preparative chromatography. Identification and quantification of the fruit extracts of four Cirsium (C.) species (C. arvense, C. canum, C. oleraceum, and C. palustre), revealed that (i) all four species do accumulate the tracheloside/trachelogenin or the arctiin/arctigenin butyrolactone-type glycoside/aglycone pairs, (ii) the overwhelming part of lignans are present as glycosides (tracheloside 9.1-14.5 mg/g, arctiin 28.6-39.3 mg/g, expressed on dry fruit basis), (iii) their acidic and enzymatic hydrolyses to the corresponding aglycones, to trachelogenin and arctigenin are fast and quantitative and (iv) the many-sided beneficial trachelogenin and arctigenin can be prepared separately, without impurities, excellent for medicinal purposes. PMID:20813375

Boldizsár, I; Kraszni, M; Tóth, F; Noszál, B; Molnár-Perl, I

2010-10-01

100

A comparison of the validity of gas chromatography- mass spectrometry and liquid chromatography- tandem mass spectrometry analysis of urine samples for morphine, codeine, 6-acetylmorphine, and benzoylecgonine.  

PubMed

On November 25, 2008, the U.S. Department of Health and Human Services posted a final notice in the Federal Register authorizing the use of liquid chromatography-tandem mass spectrometry (LC-MS-MS) and other technologies in federally regulated workplace drug testing (WPDT) programs. These rules are expected to become effective in May 2010. To support this change, it is essential to explicitly demonstrate that LC-MS-MS as a technology can produce results at least as valid as gas chromatography-mass spectrometry (GC-MS), the long-accepted standard in confirmatory analytical technologies for drugs of abuse and currently the only confirmatory method allowed for use in support of federally regulated WPDT programs. A series of manufactured control urine samples (n = 10 for each analyte) containing benzoylecgonine, morphine, codeine, and 6-acetylmorphine at concentrations ranging from 10% to 2000% of federal cutoffs were analyzed with replication by five federally regulated laboratories using GC-MS (five replicate analyses per lab) and at RTI International using LC-MS-MS (10 replicate analyses). Interference samples as described in the National Laboratory Certification Program 2009 Manual were also analyzed by both GC-MS and LC-MS-MS. In addition, matrix effects were assessed for LC-MS-MS, and both analytical technologies were used to analyze previously confirmed urine specimens of WPDT origin. Results indicated that LC-MS-MS analysis produced results at least as precise, accurate, and specific as GC-MS for the analytes investigated in this study. Matrix effects, while evident, could be controlled by the use of matrix-matched controls and calibrators with deuterated internal standards. LC-MS-MS data parameters, such as retention time and product ion ratios, were highly reproducible. PMID:19874645

Stout, Peter R; Bynum, Nichole D; Mitchell, John M; Baylor, Michael R; Ropero-Miller, Jeri D

2009-10-01

101

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

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

Tang, Yinjie; Pingitore, Francesco; Mukhopadhyay, Aindrila; Phan, Richard; Hazen, Terry C.; Keasling, Jay D.

2007-01-01

102

Quantifying biomass composition by gas chromatography/mass spectrometry.  

PubMed

We developed a set of methods for the quantification of four major components of microbial biomass using gas chromatography/mass spectrometry (GC/MS). Specifically, methods are described to quantify amino acids, RNA, fatty acids, and glycogen, which comprise an estimated 88% of the dry weight of Escherichia coli. Quantification is performed by isotope ratio analysis with fully (13)C-labeled biomass as internal standard, which is generated by growing E. coli on [U-(13)C]glucose. This convenient, reliable, and accurate single-platform (GC/MS) workflow for measuring biomass composition offers significant advantages over existing methods. We demonstrate the consistency, accuracy, precision, and utility of this procedure by applying it to three metabolically unique E. coli strains. The presented methods will have widespread applicability in systems microbiology and bioengineering. PMID:25208224

Long, Christopher P; Antoniewicz, Maciek R

2014-10-01

103

Specialized Gas Chromatography--Mass Spectrometry Systems for Clinical Chemistry.  

ERIC Educational Resources Information Center

A discussion of the basic design and characteristics of gas chromatography-mass spectrometry systems used in clinical chemistry. A comparison of three specific systems: the Vitek Olfax IIA, Hewlett-Packard HP5992, and Du Pont DP-102 are included. (BB)

Gochman, Nathan; And Others

1979-01-01

104

Microextraction and Gas Chromatography/Mass Spectrometry for improved analysis of geosmin and other fungal "off" volatiles in grape juice.  

PubMed

Geosmin is a volatile fungal metabolite with an earthy aroma produced in grape products from rotten grapes. The accumulation of geosmin in grapes is caused by the interaction of Botrytis cinerea and Penicillium expansum. Solid Phase Microextraction (SPME) has great utility for collecting volatile compounds in wine. However, contamination with earthy odours may have occurred previously in the must and novel methods are required for this commodity. In the present report, several parameters of the SPME were evaluated to optimize geosmin extraction. The method permitted quantification of geosmin and other fungal volatiles by Gas Chromatography-Mass Spectrometer (GC-MS) at very low concentrations. Limits of detection and quantification (L(D) and L(Q)) for geosmin were 4.7 ng L(-1) and 15.6 ng L(-1) respectively. The RSD was 4.1% and the recovery rates ranged from 115% to 134%. Uniquely, haloanisoles were analyzed by using only one internal standard (2,3,6-trichloroanisole) thus avoiding the synthesis of deuterated anisole analogues that are used as internal standard in other methods. The method was used for the analysis of grape juice samples inoculated with B. cinerea and P. expansum. Geosmin and methylisoborneol were the compounds that appeared to contribute most to earthy odours, although other fungal compounds which are claimed to cause earthy or mouldy off-odours were detected (e.g. 1-octen-3-ol and fenchol). PMID:20655340

Morales-Valle, H; Silva, L C; Paterson, R R M; Oliveira, J M; Venâncio, A; Lima, N

2010-10-01

105

Monitoring sulfur mustard exposure by gas chromatography-mass spectrometry analysis of thiodiglycol cleaved from blood proteins.  

PubMed

A gas chromatography-mass spectrometry method for determining exposure to the chemical warfare agent 2,2'-dichlorodiethyl sulfide (sulfur mustard; HD) has been developed. The technique is based upon quantitating thiodiglycol (TDG) released from blood protein adducts that are formed upon exposure to HD. Protein was precipitated from plasma, whole blood, or packed red blood cells (RBCs) and then treated with sodium hydroxide to liberate protein-bound TDG. The TDG was derivatized with pentafluorobenzoyl chloride that enabled sensitive detection by negative-ion chemical ionization. Octadeuterothiodiglycol was used as an internal standard. Exposure of human plasma to HD (25 nM to 400 nM) resulted in a linear relationship (r2 = 0.9995) between HD concentration and released TDG levels with means ranging from 2.0 to 38 pg/mg protein. The coefficients of variation expressed as a percentage for the data points ranged from 2 to 11.5%. The application of this procedure was demonstrated in two HD animal exposure models. African green monkeys (Chlorocebus aethiops) were exposed intravenously to 1 mg/kg HD, and TDG levels in blood samples were analyzed out to 45 days post-exposure. Mean TDG levels were determined to be 220 pg/mg protein on day 1 and declined to 10 pg/mg protein on day 45. Yorkshire cross pigs (Sus scrofa) were cutaneously exposed to neat liquid HD, and TDG levels in plasma were determined out to 21 days following exposure. Mean TDG levels were found to be 60 pg/mg protein on day one and decreased to an average of 4 pg/mg protein on day 21. The data from this study indicate that the assay is sensitive and provide a relatively simple approach to assay TDG cleaved from blood proteins at relatively long time frames (21-45 days) after HD exposure. The utility of the method has been demonstrated in vivo in a non-human primate and pig HD exposure model. PMID:15239847

Capacio, Benedict R; Smith, J R; DeLion, Michael T; Anderson, Dana R; Graham, John S; Platoff, Gennady E; Korte, William D

2004-01-01

106

Molecularly imprinted fibers with renewable surface for solid-phase microextraction of triazoles from grape juice samples followed by gas chromatography mass spectrometry analysis.  

PubMed

This paper describes the synthesis and characterization of a new molecularly imprinted solid-phase microextraction fiber able to renew its selective binding sites because of the gradual thermal decomposition of the polymeric network. The injector of the chromatograph operates at 300 °C, and during the desorption step of the analytes (in a short period), the polymeric network is degraded from the surface to the core in volatile compounds that do not interfere with the analysis. The renewable MIP fiber was successfully employed to extract triazole fungicides (triadimenol, tebuconazole, and metconazole) from grape juice samples followed by gas chromatography mass spectrometry analysis. The method was adjusted to the quadratic models from 100 to 2000 ?g L(-1), with good precision and accuracy. The limits of quantification (100 ?g L(-1) for all analytes) were sufficient to analyze triadimenol, tebuconazole, and metconazole in grape juice samples, where their maximum residue limits in Brazil are 100, 2000, and 1000 ?g L(-1), respectively. PMID:24317365

Freitas, Lissara Aparecida de Souza; Vieira, André Coutinho; Mendonça, João Antônio Felipe Risolia; Figueiredo, Eduardo Costa

2014-02-01

107

Preparation of durable graphene-bonded titanium fibers for efficient microextraction of phthalates from aqueous matrices and analysis with gas chromatography-mass spectrometry.  

PubMed

A solid-phase microextraction fiber (SPME) was synthesized for pre-concentration of 15 phthalates from aqueous samples. Graphene oxide was immobilized on Ti wire with titanol groups using a cross-linking agent and subsequently reduced to yield a folded and wrinkled graphene coating. This graphene-Ti fiber demonstrated durable mechanical robustness and enhanced stability for more than 200 extraction cycles due to the Ti substrate and chemical bond. The extraction efficiencies reached highest when the graphene layers were four and their performances were superior to commercial SPME fibers. The prepared fiber was used for pre-concentration of phthalates from aqueous samples by direct immersion extraction and thermal desorption for gas chromatography-mass spectrometry analysis. The method was utilized for the simultaneous analysis of 15 phthalates with satisfactory recoveries in the range of 82.8-97.8% for bottled water and 73.3-102.0% for intravenous drips in plastic packaging. PMID:25454125

Zhang, Bo-Tao; Li, Hai-Fang; Zheng, Xiaoxia; Teng, Yanguo; Liu, Yan; Lin, Jin-Ming

2014-11-28

108

Comparative analysis of Pu-erh and Fuzhuan teas by fully automatic headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry and chemometric methods.  

PubMed

Thirteen Pu-erh teas and 13 Fuzhuan teas obtained from two different production areas in China were profiled using fully automatic headspace solid-phase microextraction (HS-SPME)/gas chromatography-mass spectrometry (GC-MS) coupled with chemometric methods. A total of 93 aroma components were identified in 26 dark teas; among them, methoxyphenolic compounds (31.77%) were the most abundant components in Pu-erh teas, whereas ketone compounds were the most abundant components (25.42%) in Fuzhuan teas. Cluster analysis (CA) and principal component analysis (PCA) showed that these two types of dark teas could be clearly distinguished according to their chemical characteristics. This study suggested that the proposed strategy could provide a feasible and rapid technique to differentiate dark teas with similar morphological characteristics from different production areas by their volatile composition and relative content. PMID:24512533

Lv, Shidong; Wu, Yuanshuang; Li, Changwen; Xu, Yongquan; Liu, Lun; Meng, Qingxiong

2014-02-26

109

Analysis of polycyclic aromatic hydrocarbons in contaminated soil by Curie point pyrolysis coupled to gas chromatography-mass spectrometry, an alternative to conventional methods.  

PubMed

Curie point pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) has been compared with classical extraction procedures (Soxhlet, sonication, KOH digestion, microwave-assisted) followed by GC-MS analysis for the determination of polycyclic aromatic hydrocarbons (PAHs) in contaminated soil. In each case, the efficiency of the technique was examined for 16 PAHs included in the US Environmental Protection Agency Priority Pollutant List. The results indicate that the recovery of PAHs is dependent on the extraction technique. The highest recoveries of PAHs were obtained with Curie point pyrolysis and KOH digestion. Py-GC-MS appeared to be interesting alternative method for the determination of PAHs in contaminated soil. The results were validated by certified soil (CRM 104) analysis. PMID:14763749

Buco, S; Moragues, M; Doumenq, P; Noor, A; Mille, G

2004-02-13

110

Analysis of alkali-lignin in a paper mill effluent decolourised with two Streptomyces strains by gas chromatography-mass spectrometry after cupric oxide degradation.  

PubMed

Alkali-lignin samples obtained from an untreated paper mill effluent and from the effluent decolourised by the strains Streptomyces avermitilis CECT 3339 and Streptomyces scabies UAH 51 were analysed by gas chromatography-mass spectrometry (GC-MS) after cupric oxide degradation. The analysis of the depolymerisation products of the alkali-lignin from the decolourised effluents showed a strain specific modification of the aromatic moiety of the alkali-lignin. Moreover, both strains were able to breakdown the aryl-alkyl ether linkages between the cinnamic acids and the lignin. Finally, GC-MS analysis showed that both strains oxidised the alkali-lignin regardless of its initial degree of oxidation. PMID:11442046

Hemández, M; Hernández-Coronado, M J; Montiel, M D; Rodríguez, J; Arias, M E

2001-06-15

111

Gas chromatography-mass spectrometry and high-performance liquid chromotagraphy analysis of the drug absorption characteristics in the buccal mucosa via a circulating device.  

PubMed

The aim of the present study was to investigate the characteristics of Su Xiao Jiu Xin dripping pill absorption in the buccal mucosa of healthy volunteers. This pill is a traditional Chinese medicine that is widely used as an emergency treatment for cardiovascular and cerebrovascular diseases. It is sublingually administered and can be absorbed in the buccal mucosa. In the present study, a method was developed to investigate the absorption characteristics in the buccal mucosa of healthy volunteers via a circulating device by gas chromatography-mass spectrometry and high-performance liquid chromatography. The five main efficacy components associated with cardiovascular and cerebrovascular diseases, which are borneol, isoborneol, ligustilide, n-butylphthalide and ferulic acid, were detected and rapidly absorbed. Among these components, four exhibited good absorption, thus confirming that the method developed is efficient for analysis of the absoption characteristics. PMID:25469246

Wu, Xin; Li, Yubo; Xu, Daoqing; Zhou, Hong; Wang, Jinlei; Guo, Xuejun; Zhang, Yanjun

2015-01-01

112

Gas chromatography-mass spectrometry and high-performance liquid chromotagraphy analysis of the drug absorption characteristics in the buccal mucosa via a circulating device  

PubMed Central

The aim of the present study was to investigate the characteristics of Su Xiao Jiu Xin dripping pill absorption in the buccal mucosa of healthy volunteers. This pill is a traditional Chinese medicine that is widely used as an emergency treatment for cardiovascular and cerebrovascular diseases. It is sublingually administered and can be absorbed in the buccal mucosa. In the present study, a method was developed to investigate the absorption characteristics in the buccal mucosa of healthy volunteers via a circulating device by gas chromatography-mass spectrometry and high-performance liquid chromatography. The five main efficacy components associated with cardiovascular and cerebrovascular diseases, which are borneol, isoborneol, ligustilide, n-butylphthalide and ferulic acid, were detected and rapidly absorbed. Among these components, four exhibited good absorption, thus confirming that the method developed is efficient for analysis of the absoption characteristics. PMID:25469246

WU, XIN; LI, YUBO; XU, DAOQING; ZHOU, HONG; WANG, JINLEI; GUO, XUEJUN; ZHANG, YANJUN

2015-01-01

113

Method development for the analysis of 1,4-dioxane in drinking water using solid-phase extraction and gas chromatography-mass spectrometry.  

PubMed

1,4-Dioxane has been identified as a probable human carcinogen and an emerging contaminant in drinking water. The United States Environmental Protection Agency's (U.S. EPA) National Exposure Research Laboratory (NERL) has developed a method for the analysis of 1,4-dioxane in drinking water at ng/L concentrations. The method consists of an activated carbon solid-phase extraction of 500-mL or 100-mL water samples using dichloromethane as the elution solvent. The extracts are analyzed by gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. In the NERL laboratory, recovery of 1,4-dioxane ranged from 94-110% in fortified laboratory reagent water and recoveries of 96-102% were demonstrated for fortified drinking water samples. The relative standard deviations for replicate analyses were less than 6% at concentrations exceeding the minimum reporting level. PMID:19161654

Grimmett, Paul E; Munch, Jean W

2009-01-01

114

A rapid and definitive diagnosis of kerosene dermatitis by an analysis of detached lesional epidermis using gas chromatography-mass spectrometry.  

PubMed

A 73-year-old woman, who suffered from erythema with bullae and pustules on her abdomen and anterior right thigh, visited our hospital without an awareness of the causative agents. The lesions appeared like first and second degree burns. The small amount of detached roof of bulla was sampled without skin biopsy before the ointment treatment. The sample was sonicated in an ultrasonic bath for 1 min in n-pentane, and then 1 mul of the extract was analyzed by gas chromatography-mass spectrometry (GC-MS). The causative agent was determined to be kerosene. An examination of blood samples collected at the first visit failed to detect kerosene, though traces of trimethylbenzene were detected. A GC-MS analysis of the small sample of lesional epidermis was very useful to identify kerosene as a causative agent. PMID:15902481

Tsujino, Yoshio; Hieda, Yoko; Morita, Eishin

2005-08-01

115

Quantitative Analysis of Bisphenol A Leached from Household Plastics by Solid-Phase Microextraction and Gas Chromatography-Mass Spectrometry (SPME-GC-MS)  

ERIC Educational Resources Information Center

The measurement of trace levels of bisphenol A (BPA) leached out of household plastics using solid-phase microextraction (SPME) with gas chromatography-mass spectrometry (GC-MS) is reported here. BPA is an endocrine-disrupting compound used in the industrial manufacture of polycarbonate plastic bottles and epoxy resin can liners. This experiment…

Johnson, Bettie Obi; Burke, Fernanda M.; Harrison, Rebecca; Burdette, Samantha

2012-01-01

116

Analysis of fragrance composition in three cultivars of Osmanthus fragrans Albus group flower by gas chromatography-mass spectrometry  

Microsoft Academic Search

With supercritical CO2 fluid extraction(SCFE), essential oil was extracted from three cultivars of Xianning osmanthus. The fresh osmanthus flower\\u000a was processed with a petroleum ether digestion method to produce the extractum. The yields of essential oil and extractum\\u000a were 0.19 % and 0.13 % (m\\/m) respectively. The essential oil and fragrance composition and content extracted were analyzed with gas chromatography-mass

Fafang Li; Qizhi Huang

2011-01-01

117

Triclosan and methyl-triclosan monitoring study in the northeast of Spain using a magnetic particle enzyme immunoassay and confirmatory analysis by gas chromatography mass spectrometry  

NASA Astrophysics Data System (ADS)

SummaryFor the first time, the occurrence of triclosan and its metabolite methyl-triclosan was investigated in a typical Mediterranean area using a two-step methodology based on screening using a magnetic particle immunoassay (IA) and confirmatory analysis by solid phase extraction (SPE) followed by gas chromatography-mass spectrometry (GC-MS). In this study, 95 environmental samples were analyzed. A commercial immunoassay was assessed for use in the different types of water selected for this study. A large monitoring study was performed on the influent and the effluent of eight wastewater treatment plants (WWTPs), water samples from Ebro and Llobregat rivers, and drinking water. All wastewater samples tested in this study (influents and effluents) showed the presence of triclosan, with concentrations for raw influents being high (10 ?g/L as average value). The percentages of triclosan removal for the WWTPs were evaluated (30-70%) along the different treatment processes showing that the best removal rates were obtained by the processes equipped with membrane bioreactors (MBRs). However, important concentrations of triclosan were detected even after treatment by MBRs. The presence of this biocide was confirmed in 50% of the river samples analyzed. Twenty two drinking water samples from the Barcelona city area were investigated, and in this case no triclosan was detected. Due to its properties and the widespread usage of triclosan, there is a need for monitoring and controlling the amounts present in wastewater effluents, river water, drinking water catchments areas, and drinking water. To this end, we present a feasible methodology using a magnetic particle-based immunoassay as a screening, followed by confirmatory analysis using solid phase extraction-gas chromatography-mass spectrometry (SPE-GC-MS).

Kantiani, Lina; Farré, Marinella; Asperger, Danijela; Rubio, Fernando; González, Susana; López de Alda, Maria J.; Petrovi?, Mira; Shelver, Weilin L.; Barceló, Damià

2008-10-01

118

A METHOD FOR AUTOMATED ANALYSIS OF 10 ML WATER SAMPLES CONTAINING ACIDIC, BASIC, AND NEUTRAL SEMIVOLATILE COMPOUNDS LISTED IN USEPA METHOD 8270 BY SOLID PHASE EXTRACTION COUPLED IN-LINE TO LARGE VOLUME INJECTION GAS CHROMATOGRAPHY/MASS SPECTROMETRY  

EPA Science Inventory

Data is presented showing the progress made towards the development of a new automated system combining solid phase extraction (SPE) with gas chromatography/mass spectrometry for the single run analysis of water samples containing a broad range of acid, base and neutral compounds...

119

Assessment of a new method for the analysis of decomposition gases of polymers by a combining thermogravimetric solid-phase extraction and thermal desorption gas chromatography mass spectrometry.  

PubMed

For analysis of the gaseous thermal decomposition products of polymers, the common techniques are thermogravimetry, combined with Fourier transformed infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). These methods offer a simple approach to the decomposition mechanism, especially for small decomposition molecules. Complex spectra of gaseous mixtures are very often hard to identify because of overlapping signals. In this paper a new method is described to adsorb the decomposition products during controlled conditions in TGA on solid-phase extraction (SPE) material: twisters. Subsequently the twisters were analysed with thermal desorption gas chromatography mass spectrometry (TDS-GC-MS), which allows the decomposition products to be separated and identified using an MS library. The thermoplastics polyamide 66 (PA 66) and polybutylene terephthalate (PBT) were used as example polymers. The influence of the sample mass and of the purge gas flow during the decomposition process was investigated in TGA. The advantages and limitations of the method were presented in comparison to the common analysis techniques, TGA-FTIR and TGA-MS. PMID:24929909

Duemichen, E; Braun, U; Senz, R; Fabian, G; Sturm, H

2014-08-01

120

Application of gas chromatography-mass spectrometry metabolite profiling techniques to the analysis of heathland plant diets of sheep.  

PubMed

Little is known about how plant biochemistry influences the grazing behavior of animals consuming heterogeneous plant communities. The biochemical profiles of grassland species are mostly restricted to major nutritional characteristics, although recent developments in analytical techniques and data analysis have made possible the detailed analysis of minor components that may influence animal feeding preferences, performance, and health. In the present study, gas chromatography coupled with time-of-flight mass spectrometry (GC-TOF/MS) was used to profile the abundances of metabolites in nine specific heathland plant groups and in three mixed forage diets containing 10, 20, or 30% heather (Calluna vulgaris) and also in plasma and feces from sheep offered one of the three diets. Statistical and chemometric approaches, that is, principal component analysis (PCA) and hierarchical cluster analysis (HCA), were used to discriminate between these diets and between individual animals maintained on these diets. It is shown that GC-TOF/MS analysis of sheep plasma allowed distinction between the very similar diets by PCA and HCA, and, moreover, the plant metabolites responsible for the differences observed have been identified. Furthermore, metabolite markers of herbage mixtures and individual plant groups have been identified, and markers have been detected in sheep plasma and feces. PMID:17249687

Parveen, Ifat; Moorby, Jon M; Fraser, Mariecia D; Allison, Gordon G; Kopka, Joachim

2007-02-21

121

Identification of Synthetic Polymers and Copolymers by Analytical Pyrolysis-Gas Chromatography/Mass Spectrometry  

ERIC Educational Resources Information Center

An experiment for the identification of synthetic polymers and copolymers by analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was developed and performed in the polymer analysis courses for third-year undergraduate students of chemistry with material sciences, and for first-year postgraduate students of polymer sciences. In…

Kusch, Peter

2014-01-01

122

Current Applications of Gas Chromatography\\/Mass Spectrometry in the Study of Organic Acids in Urine  

Microsoft Academic Search

Gas chromatography\\/mass spectrometry (GC\\/MS) is the most suitable technique for the diagnosis of disorders of organic acid metabolism, known as organic acidurias. They are inherited metabolic disorders that are characterized by an excessive amount of organic acids and their metabolites. Now in many clinical and diagnostic laboratories, automated, quantitative, and qualitative procedures for complex mixture analysis of urinary organic acids

Joanna Kauna-Czapli?ska

2011-01-01

123

Comparative Analysis of the Volatile Components of Agrimonia eupatoria from Leaves and Roots by Gas Chromatography-Mass Spectrometry and Multivariate Curve Resolution.  

PubMed

Gas chromatography-mass spectrometry and multivariate curve resolution were applied to the differential analysis of the volatile components in Agrimonia eupatoria specimens from different plant parts. After extracted with water distillation method, the volatile components in Agrimonia eupatoria from leaves and roots were detected by GC-MS. Then the qualitative and quantitative analysis of the volatile components in the main root of Agrimonia eupatoria was completed with the help of subwindow factor analysis resolving two-dimensional original data into mass spectra and chromatograms. 68 of 87 separated constituents in the total ion chromatogram of the volatile components were identified and quantified, accounting for about 87.03% of the total content. Then, the common peaks in leaf were extracted with orthogonal projection resolution method. Among the components determined, there were 52 components coexisting in the studied samples although the relative content of each component showed difference to some extent. The results showed a fair consistency in their GC-MS fingerprint. It was the first time to apply orthogonal projection method to compare different plant parts of Agrimonia eupatoria, and it reduced the burden of qualitative analysis as well as the subjectivity. The obtained results proved the combined approach powerful for the analysis of complex Agrimonia eupatoria samples. The developed method can be used to further study and quality control of Agrimonia eupatoria. PMID:24286016

Feng, Xiao-Liang; He, Yun-Biao; Liang, Yi-Zeng; Wang, Yu-Lin; Huang, Lan-Fang; Xie, Jian-Wei

2013-01-01

124

Comparative Analysis of the Volatile Components of Agrimonia eupatoria from Leaves and Roots by Gas Chromatography-Mass Spectrometry and Multivariate Curve Resolution  

PubMed Central

Gas chromatography-mass spectrometry and multivariate curve resolution were applied to the differential analysis of the volatile components in Agrimonia eupatoria specimens from different plant parts. After extracted with water distillation method, the volatile components in Agrimonia eupatoria from leaves and roots were detected by GC-MS. Then the qualitative and quantitative analysis of the volatile components in the main root of Agrimonia eupatoria was completed with the help of subwindow factor analysis resolving two-dimensional original data into mass spectra and chromatograms. 68 of 87 separated constituents in the total ion chromatogram of the volatile components were identified and quantified, accounting for about 87.03% of the total content. Then, the common peaks in leaf were extracted with orthogonal projection resolution method. Among the components determined, there were 52 components coexisting in the studied samples although the relative content of each component showed difference to some extent. The results showed a fair consistency in their GC-MS fingerprint. It was the first time to apply orthogonal projection method to compare different plant parts of Agrimonia eupatoria, and it reduced the burden of qualitative analysis as well as the subjectivity. The obtained results proved the combined approach powerful for the analysis of complex Agrimonia eupatoria samples. The developed method can be used to further study and quality control of Agrimonia eupatoria. PMID:24286016

Feng, Xiao-Liang; He, Yun-biao; Liang, Yi-Zeng; Wang, Yu-Lin; Huang, Lan-Fang; Xie, Jian-Wei

2013-01-01

125

Rapid simultaneous analysis of cyclooxygenase, lipoxygenase and cytochrome P-450 metabolites of arachidonic and linoleic acids using high performance liquid chromatography\\/mass spectrometry in tandem mode  

Microsoft Academic Search

Eicosanoids are oxidized arachidonate-derived lipid products generated by cyclooxygenase, lipoxygenase and cytochrome P-450 pathways. They are involved in diverse processes in health and disease and they are highly bioactive. Gas chromatography and enzyme immunoassays were used to quantify these mediators in the past. However, the recent availability of high-sensitivity liquid chromatography–mass spectrometry has provided a new approach for quantification that

Raquel Martín-Venegas; Rosario Casillas; Olga Jáuregui; Juan José Moreno

2011-01-01

126

Analysis of Essential Oil in Jerusalem Artichoke (Helianthus tuberosus L.) Leaves and Tubers by Gas Chromatography-Mass Spectrometry  

PubMed Central

Purpose: To investigate, for the first time, the chemical composition of essential oil of the tubers and leaves of Jerusalem artichoke (Helianthus tuberosus L.), a species of sunflower native to eastern North America, growing in Ukraine. Methods: A hydrodistillation apparatus was used for the extraction of volatile components and then it was analysed by gas chromatography equipped with a split-splitless injector (split ratio, 1:50) and flame ionization detector (FID). The oil was analyzed under linear temperature programming applied at 4°C/min from 50°C - 340°C. Temperatures of the injector and FID detector were maintained at 280°C and 300°C, respectively. The chemical analysis of the oil was carried out using gas chromatography coupled to mass spectrometry (GC-MS), to determine the chemical composition of the volatile fraction. Results: The essential oils content ranged from 0.00019 to 0.03486 and 0.00011 to 0.00205 (g/100g), in leaves and tubers, respectively. The qualitative and quantitative analysis led to the identification of 17 components in both species samples. The major component found in leaves and tubers was (-)-?-bisabolene with 70.7% and 63.1%, respectively. Conclusion: Essential oil profile of Jerusalem artichoke species showed significant differences between leaves and tubers species. Additionally, the leaves of Jerusalem artichoke are a promising source of natural ?-bisabolene. PMID:25671184

Helmi, Zead; Al Azzam, Khaldun Mohammad; Tsymbalista, Yuliya; Ghazleh, Refat Abo; Shaibah, Hassan; Aboul-Enein, Hassan

2014-01-01

127

A NEW METHOD OF PEAK DETECTION FOR ANALYSIS OF COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY MASS SPECTROMETRY DATA*  

PubMed Central

We develop a novel peak detection algorithm for the analysis of comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC-TOF MS) data using normal-exponential-Bernoulli (NEB) and mixture probability models. The algorithm first performs baseline correction and denoising simultaneously using the NEB model, which also defines peak regions. Peaks are then picked using a mixture of probability distribution to deal with the co-eluting peaks. Peak merging is further carried out based on the mass spectral similarities among the peaks within the same peak group. The algorithm is evaluated using experimental data to study the effect of different cut-offs of the conditional Bayes factors and the effect of different mixture models including Poisson, truncated Gaussian, Gaussian, Gamma, and exponentially modified Gaussian (EMG) distributions, and the optimal version is introduced using a trial-and-error approach. We then compare the new algorithm with two existing algorithms in terms of compound identification. Data analysis shows that the developed algorithm can detect the peaks with lower false discovery rates than the existing algorithms, and a less complicated peak picking model is a promising alternative to the more complicated and widely used EMG mixture models. PMID:25264474

Kim, Seongho; Ouyang, Ming; Jeong, Jaesik; Shen, Changyu; Zhang, Xiang

2014-01-01

128

A NEW METHOD OF PEAK DETECTION FOR ANALYSIS OF COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY MASS SPECTROMETRY DATA.  

PubMed

We develop a novel peak detection algorithm for the analysis of comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC-TOF MS) data using normal-exponential-Bernoulli (NEB) and mixture probability models. The algorithm first performs baseline correction and denoising simultaneously using the NEB model, which also defines peak regions. Peaks are then picked using a mixture of probability distribution to deal with the co-eluting peaks. Peak merging is further carried out based on the mass spectral similarities among the peaks within the same peak group. The algorithm is evaluated using experimental data to study the effect of different cut-offs of the conditional Bayes factors and the effect of different mixture models including Poisson, truncated Gaussian, Gaussian, Gamma, and exponentially modified Gaussian (EMG) distributions, and the optimal version is introduced using a trial-and-error approach. We then compare the new algorithm with two existing algorithms in terms of compound identification. Data analysis shows that the developed algorithm can detect the peaks with lower false discovery rates than the existing algorithms, and a less complicated peak picking model is a promising alternative to the more complicated and widely used EMG mixture models. PMID:25264474

Kim, Seongho; Ouyang, Ming; Jeong, Jaesik; Shen, Changyu; Zhang, Xiang

2014-06-01

129

Analysis of cocaine and benzoylecgonine in urine by using multisyringe flow injection analysis-gas chromatography-mass spectrometry system.  

PubMed

In this paper, a method was described to determine cocaine (COC) and benzoylecgonine (BZE) in human urine samples by GC-MS detection. The extraction of analytes from urine samples was achieved in an Oasis hydrophilic-lipophilic balance column (20 mmx3.9 mm id, dp=25 microm; Waters, USA), incorporated in a multisyringe flow injection system, used for the sample treatment. Finally, to improve the volatility of the BZE, an in-line derivatization reaction with N,O-bis (trimethylsilyl) trifluoroacetamide with 1% trimethylchlorosilane was made microwave-assisted in order to reduce the reaction time. The results showed that the proposed method is a good alternative for the analysis of COC and BZE in urine samples because it offers advantages compared with those described in the literature, which include simplicity in the sample treatment, the sensitivity and selectivity necessary to determine the analytes of interest at low levels in the urine and high sample throughput. PMID:20491055

Brunetto, María del Rosario; Delgado, Yelitza; Clavijo, Sabrina; Contreras, Yaritza; Torres, Dina; Ayala, Carlos; Gallignani, Máximo; Forteza, Rafael; Cerdà Martin, Víctor

2010-06-01

130

Metabolic flux analysis of Arthrobacter sp. CGMCC 3584 for cAMP production based on 13C tracer experiments and gas chromatography-mass spectrometry.  

PubMed

Arthrobacter sp. CGMCC 3584 are able to produce cAMP from glucose by the purine synthesis pathway via de novo or salvage biosynthesis. In order to gain an improved understanding of its metabolism, (13)C-labeling experiment and gas chromatography-mass spectrometry (GC-MS) analysis were employed to determine the metabolic network structure and estimate the intracellular fluxes. GC-MS analysis helps to reflect the activity of the intracellular pathways and reactions. The metabolic network mainly contains glycolytic and pentose phosphate pathways, the tricarboxylic acid cycle, and the inactive glyoxylate shunt. Hypoxanthine as a precursor of cAMP and sodium fluoride as an inhibitor of glycolysis were found to increase the cAMP production, as well as the flux through the PP pathway. The effects of adding hypoxanthine and sodium fluoride are discussed based on the enzyme assays and metabolic flux analysis. In conclusion, our results provide quantitative insights into how cells manipulate the metabolic network under different culture conditions and this may be of value in metabolic regulation for desirable production. PMID:24056081

Niu, Huanqing; Chen, Yong; Yao, Shiwei; Liu, Lixia; Yang, Chen; Li, Bingbing; Liu, Dong; Xie, Jingjing; Chen, Xiaochun; Wu, Jinglan; Ying, Hanjie

2013-12-01

131

Cortisol production rates measured by liquid chromatography/mass spectrometry  

SciTech Connect

Cortisol production rates (FPRs) in physiologic and pathologic states in humans have been investigated over the past 30 years. However, there has been conflicting evidence concerning the validity of the currently accepted value of FPRs in humans (12 to 15 mg/m2/d) as determined by radiotracer methodology. The present study reviews previous methods proposed for the measurement of FPRs in humans and discusses the applications of the first method for the direct determination of 24-hour plasma FPRs during continuous administration of a stable isotope, using a thermospray high-pressure liquid chromatography-mass spectrometry technique. The technique is fast, sensitive, and, unlike gas chromatography-mass spectrometry methods, does not require derivatization, allowing on-line detection and quantification of plasma cortisol after a simple extraction procedure. The results of determination of plasma FPRs by stable tracer/mass spectrometry are directly in units of mass/time and, unlike radiotracer methods, are independent of any determination of volume of distribution or cortisol concentration. Our methodology offers distinct advantages over radiotracer techniques in simplicity and reliability since only single measurements of isotope ratios are required. The technique was validated in adrenalectomized patients. Circadian variations in daily FRPs were observed in normal volunteers, and, to date, results suggest a lower FRP in normal children and adults than previously believed. 88 references.

Esteban, N.V.; Yergey, A.L. (National Institute of Child Health and Human Development, Bethesda, MD (USA))

1990-04-01

132

Signal and Charge Enhancement for Protein Analysis by Liquid Chromatography-Mass Spectrometry with Desorption Electrospray Ionization  

PubMed Central

We recently reported the use of desorption electrospray ionization (DESI) as a novel interface to couple high-performance liquid chromatography (HPLC) with mass spectrometry (MS) (Chem. Commun. 2011, 47, 4171). One of the benefits of such an interface is that post-column derivatization of separated analytes can be integrated with ionization via a “reactive” DESI approach in which a derivatizing reagent is doped into the spray solvent. The reactive DESI interface allows analyte desorption/ionization from the end of the chromatographic column with prompt MS detection; a short time delay of ~20 ms was demonstrated. In this study, we extended this application by “supercharging” proteins following HPLC separation using a DESI spray solvent containing supercharging reagents, m-nitrobenzyl alcohol (m-NBA) or sulfolane. Proteins (insulin, ubiquitin, lysozyme and ?-lactalbumin) eluted out of the LC column can be supercharged with the protein charge state distributions (CSDs) significantly increased (to higher charge), which would be advantageous for subsequent top-down MS analysis of proteins. Interestingly, supercharging combined with reactive DESI enhances tolerance towards trifluoroacetic acid (TFA), which is known to be a superior additive in the mobile phase for premium peptide/protein chromatographic separation but has severe signal suppression effects for conventional electrospray ionization (ESI). In comparison to electrosonic spray ionization (ESSI), a variant form of ESI, the sensitivity of protein analysis using LC/DESI-MS with the mobile phase containing TFA can be improved by up to 70-fold for lysozyme and ?-lactalbumin by including m-NBA in the DESI spray solvent. Presumably, by reducing TFA dissociation in the droplet, supercharging agents lower trifluoroacetate anion concentrations and concomitantly reduce ion pairing to analyte cationic sites. The reduced ion pairing therefore decreases the TFA signal suppression effect. The supercharging capability and the reduction of TFA signal suppression suggest that LC/DESI-MS is a valuable method for protein analysis.

Liu, Yan; Miao, Zhixin; Lakshmanan, Rajeswari; Ogorzalek Loo, Rachel R.; Loo, Joseph A.; Chen, Hao

2015-01-01

133

Recent applications of liquid chromatography-mass spectrometry to residue analysis of antimicrobials in food of animal origin.  

PubMed

Residual antimicrobials in food constitute a risk to human health. Although epidemiological data on the real magnitude of their adverse effects are very scarce, they indicate that food could be an important vehicle for evolution and dissemination of antimicrobial-resistant bacteria. Public health agencies in many countries rely on detection by mass spectrometry (MS) for unambiguous identification of residues of antimicrobial agents in animal food products for human consumption. The introduction of relatively inexpensive and robust liquid chromatography (LC)-MS systems has given a strong impulse to the development of confirmatory methods for the above medicines in foodstuffs. The initial part of this review, after a brief introduction into the field of antimicrobials, is dedicated to the most important EU regulations and directives for control of residues of these substances in animal products. The main attention in this review is on the sample-treatment and MS detection systems in use today for analysing the most important classes of antimicrobials in various biological matrices (milk, animal tissues, eggs, and honey). As evidenced by this review, reversed-phase LC combined with tandem MS, usually triple-quadrupole MS (QqQMS), is currently the preferred technique in most residue analysis of a single-class of antimicrobials. A recently emerging analytical strategy is that of developing methods for detecting a large variety of veterinary drugs belonging to different classes, including pesticides (multi-class residue analysis). To do this, simple and generic extraction and separation techniques applicable to a broad range of compounds differing in physical and chemical properties have been adopted. Such methods are still based mainly on LC-QqQMS. Emerging alternative MS detection systems are time-of-flight MS, which provides accurate mass of the analyte(s), or Q-linear ion trap (IT) MS that eliminates some limitations of ITMS(n). PMID:19609510

Bogialli, Sara; Di Corcia, Antonio

2009-10-01

134

Simultaneous analysis of some club drugs in whole blood using solid phase extraction and gas chromatography-mass spectrometry.  

PubMed

The use of psychoactive substances to improve social relations and increase body energy, in Rave Culture, has raised many legal and health public concerns, both for illicit trade and consumption. Therefore, forensic toxicology plays an important role in this area, mainly linked to the detection and quantitation of these substances, both in vivo and in post-mortem samples. In fact, at the moment, forensic sciences have been under public authorities' scrutiny and critical look, due to the increasing attention of the media and public opinion, always applying for the use of scientific knowledge to help solving forensic cases. However, forensic toxicology results are only reliable to solve legal cases if all the analytical methodologies used are appropriately validated. In this work, a methodology for the extraction and analysis of 7-aminoflunitrazepam, buprenorphine, flunitrazepam, ketamine, methadone, phencyclidine (PCP) and d-propoxyphene was developed for whole blood samples, with solid phase extraction (SPE), using OASIS(®) MCX SPE columns, and gas chromatography coupled to mass spectrometry. The procedure presented here proved to be reliable, specific, selective and sensitive, with good LODs and LOQs and good precision.The adoption of a SPE procedure with an automatic SPE extraction device, allowed an increased level of automation in sample treatment, being contemporarily less time-consuming, increasing productiveness, and allowing good recovery and appropriate selectivity being, also, simple and reproducible. The simultaneous detection and quantitation of all compounds by the same extraction and detection methodology is crucial and has a great potential for forensic toxicology and clinical analysis. PMID:22281215

Castro, André L; Tarelho, Sónia; Silvestre, Armando; Teixeira, Helena M

2012-02-01

135

Complex mixture analysis based on gas chromatography-mass spectrometry with time array detection using a beam deflection time-of-flight mass spectrometer.  

PubMed

A beam deflection time-of-flight mass spectrometer was developed in conjunction with an integrating transient recorder to provide time array detection, permitting high mass spectral scan file acquisition rates for complex mixture analysis by capillary gas chromatography-mass spectrometry (GC-MS). Results are presented for the analysis of a urinary organic acid mixture by GC-MS at a scan file acquisition rate of 10 scan files per second (sf/s), showing the advantages of such data collection in the deconvolution of partially resolved components. The reconstructed total ion current (RTIC) chromatogram available from data acquired at this scan file generation rate is shown to be comparable to the profile obtained from a flame ionization detector in representing the chromatography performed under identical experimental parameters. The RTIC chromatogram available from the database obtained at 10 sf/s is compared with that available from a database obtained at 1 sf/s, the latter representing that scan rate typically used with most GC-MS instruments. The advantages of the higher scan file acquisition rate in representing the chromatographic profile and in allowing mass spectral data to be obtained for components in the complex mixture that are unresolved chromatographically are discussed. PMID:1560100

Schultz, G A; Chamberlin, B A; Sweeley, C C; Watson, J T; Allison, J

1992-01-31

136

Water analysis of the sixteen environmental protection agency-polycyclic aromatic hydrocarbons via solid-phase nanoextraction-gas chromatography/mass spectrometry.  

PubMed

The growing concern with a sustainable environment poses a new challenge to analytical chemists facing the routine monitoring of polycyclic aromatic hydrocarbons (PAHs) in water samples. The new method presented here meets several features of green analytical chemistry. PAHs are extracted from 500 ?L of water sample with 1 mL of a gold nanoparticles aqueous solution and released with 100 ?L of organic solvents for subsequent analysis via gas chromatography/mass spectrometry. The relative standard deviations of the overall procedure ranged from 2.4 (acenaphthene) to 7.8% (dibenz[a,h]anthracene). The limits of detection were excellent as well and varied from 4.94 (fluoranthene) to 65.5 ng L(-1) (fluorene). The excellent analytical figures of merit, the simplicity of the experimental procedure, the short analysis time and the reduced solvent consumption demonstrate the potential of this approach for the routine monitoring of the sixteen priority pollutants via and environmentally friendly methodology. PMID:24794939

Wilson, Walter B; Hewitt, Udienza; Miller, Mattheu; Campiglia, Andres D

2014-06-01

137

Optimization of a Solid-Phase Microextraction method for the Gas Chromatography-Mass Spectrometry analysis of blackberry (Rubus ulmifolius Schott) fruit volatiles.  

PubMed

A Solid-Phase Microextraction method for the Gas Chromatography-Mass Spectrometry analysis of blackberry (Rubus sp.) volatiles has been fully optimized by means of a Box-Behnken experimental design. The optimized operating conditions (Carboxen/Polydimethylsiloxane fiber coating, 66°C, 20min equilibrium time and 16min extraction time) have been applied to the characterization for the first time of the volatile composition of Rubus ulmifolius Schott blackberries collected in Italy and Spain. A total of 74 volatiles of different functionality were identified; esters and aliphatic alcohols were the predominant classes in both sample types. Methylbutanal (2.02-25.70%), ethanol (9.84-68.21%), 2,3-butanedione (2.31-14.71%), trans-2-hexenal (0.49-17.49%), 3-hydroxy-2-butanone (0.08-7.39%), 1-hexanol (0.56-16.39%), 1-octanol (0.49-10.86%) and methylbutanoic acid (0.53-21.48%) were the major compounds in most blackberries analyzed. Stepwise multiple regression analysis of semiquantitative data showed that only two variables (ethyl decanoate and ethyl acetate) were necessary for a successful differentiation of blackberries according to their harvest location. PMID:25704677

D'Agostino, M F; Sanz, J; Sanz, M L; Giuffrè, A M; Sicari, V; Soria, A C

2015-07-01

138

A method by homemade OH/TSO-PMHS fibre solid-phase microextraction coupling with gas chromatography-mass spectrometry for analysis of antiestrogens in biological matrices.  

PubMed

A kind of homemade solid-phase microextraction fibre coupled with gas chromatography-mass spectrometry (GC-MS) was developed for trace analysis of antiestrogens (tamoxifen, cis- and trans-clomiphene) in biological matrices. In this method, derivatization was unnecessary and sample solution could be injected directly after very simple deproteinization operation. The conditions of influencing adsorption of the solid-phase microextraction (SPME) fibre and desorption of the analytes were investigated in details. Matrix effects were studied in different background. Under optimum conditions, the proposed method was further validated by spiking analytes into rabbit liver solutions. Linear ranges of tamoxifen, cis- and trans-clomiphene were 0.02-2.56, 0.08-2.56 and 0.16-2.56 ng mL(-1), respectively. The limits of quantitation were in the range of 0.02-0.16 ng mL(-1). The intra-day accuracy was ranged 96.2-106.2% and precision were in the range of 5.1-8.7%. The extraction recoveries of the antiestrogens in rabbit liver solution were between 73.8% and 113.1%, and R.S.D.s were from 3.6% to 14.1%. The results show that the homemade sol-gel coating is suitable for determination of trace antiestrogens in complex matrices. The proposed approach was proved to be rapid, simple, easy, sensitive and reproducible for trace analysis of antiestrogens in biological matrices. PMID:19046677

Liu, Wei; Zhang, Lan; Chen, Shengping; Duan, Hongbin; Chen, Xi; Wei, Zhenyi; Chen, Guonan

2009-01-01

139

Application of an automatic thermal desorption-gas chromatography-mass spectrometry system for the analysis of polycyclic aromatic hydrocarbons in airborne particulate matter.  

PubMed

The application of the thermal desorption (TD) method coupled with gas chromatography-mass spectrometry (GC-MS) to the analysis of aerosol organics has been the focus of many studies in recent years. This technique overcomes the main drawbacks of the solvent extraction approach such as the use of large amounts of toxic organic solvents and long and laborious extraction processes. In this work, the application of an automatic TD-GC-MS instrument for the determination of particle-bound polycyclic aromatic hydrocarbons (PAHs) is evaluated. This device offers the advantage of allowing the analysis of either gaseous or particulate organics without any modification. Once the thermal desorption conditions for PAH extraction were optimised, the method was verified on NIST standard reference material (SRM) 1649a urban dust, showing good linearity, reproducibility and accuracy for all target PAHs. The method has been applied to PM10 and PM2.5 samples collected on quartz fibre filters with low volume samplers, demonstrating its capability to quantify PAHs when only a small amount of sample is available. PMID:19150718

Gil-Moltó, J; Varea, M; Galindo, N; Crespo, J

2009-02-27

140

Development of a fast extraction method and optimization of liquid chromatography-mass spectrometry for the analysis of phenolic compounds in lentil seed coats.  

PubMed

A systematic set of optimization experiments was conducted to design an efficient extraction and analysis protocol for screening six different sub-classes of phenolic compounds in the seed coat of various lentil (Lens culinaris Medik.) genotypes. Different compounds from anthocyanidins, flavan-3-ols, proanthocyanidins, flavanones, flavones, and flavonols sub-classes were first optimized for use as standards for liquid chromatography mass spectrometry (LC-MS) with UV detection. The effect of maceration duration, reconstitution solvent, and extraction solvent were investigated using lentil genotype CDC Maxim. Chromatographic conditions were optimized by examining column separation efficiencies, organic composition, and solvent gradient. The results showed that a 1h maceration step was sufficient and that non-acidified solvents were more appropriate; a 70:30 acetone: water (v/v) solvent was ultimately selected. Using a Kinetex PFP column, the organic concentration, gradient, and flow rate were optimized to maximize the resolution of phenolic compounds in a short 30-min analysis time. The optimized method was applied to three lentil genotypes with different phenolic compound profiles to provide information of value to breeding programs. PMID:25173496

Mirali, Mahla; Ambrose, Stephen J; Wood, Stephen A; Vandenberg, Albert; Purves, Randy W

2014-10-15

141

Analysis of the volatile organic matter of engine piston deposits by direct sample introduction thermal desorption gas chromatography/mass spectrometry.  

PubMed

This article establishes an alternative method for the characterization of volatiles organic matter (VOM) contained in deposits of the piston first ring grooves of diesel engines using a ChromatoProbe direct sample introduction (DSI) device coupled to gas chromatography/mass spectrometry (GC/MS) analysis. The addition of an organic solvent during thermal desorption leads to an efficient extraction and a good chromatographic separation of extracted products. The method was optimized investigating the effects of several solvents, the volume added to the solid sample, and temperature programming of the ChromatoProbe DSI device. The best results for thermal desorption were found using toluene as an extraction solvent and heating the programmable temperature injector from room temperature to 300 degrees C with a temperature step of 105 degrees C. With the use of the optimized thermal desorption conditions, several components have been positively identified in the volatile fraction of the deposits: aromatics, antioxidants, and antioxidant degradation products. Moreover, this work highlighted the presence of diesel fuel in the VOM of the piston deposits and gave new facts on the absence of the role of diesel fuel in the deposit formation process. Most importantly, it opens the possibility of quickly performing the analysis of deposits with small amounts of samples while having a good separation of the volatiles. PMID:19894696

Diaby, M; Kinani, S; Genty, C; Bouchonnet, S; Sablier, M; Le Negrate, A; El Fassi, M

2009-12-01

142

Planar solid phase extraction clean-up for pesticide residue analysis in tea by liquid chromatography-mass spectrometry.  

PubMed

Efficient clean-up is indispensable for preventing matrix effects in multi-residue analysis of pesticides in food by liquid and gas chromatography (LC and GC) coupled to mass spectrometry (MS). High-throughput planar solid phase extraction (HTpSPE) was recently introduced as a new clean-up concept in residue analysis of pesticides in fruit and vegetables (C. Oellig, W. Schwack, 2011 [45]). Thin-layer chromatography (TLC) was used to completely separate pesticides from matrix compounds and to focus them into a sharp zone, followed by extraction of the target zone by the TLC-MS interface. As rather challenging matrices, tea samples were chosen in this study. Besides chlorophylls and polyphenols, high amount of caffeine is co-extracted resulting in strong matrix effects both in LC-MS and GC-MS. The former HTpSPE procedure was adapted to initial extracts of green and black tea resulting in colorless extracts nearly free of matrix effects and interferences, as shown for seven chemically representative pesticides (acetamiprid, penconazole, azoxystrobin, chlorpyrifos, pirimicarb, fenarimol, and mepanipyrim). LC-MS/MS calibration curves obtained in the range of 0.002-0.5 mg/kg from matrix-matched standards and solvent standards were nearly identical and demonstrated the effectiveness of clean-up by HTpSPE. Mean recoveries determined by LC-MS/MS against solvent standards at spiking levels of 0.01 and 0.1 mg/kg ranged between 72 and 114% with relative standard deviations (RSDs) of 0.7-4.7% (n=4), while LC-MS measurements of tea samples spiked at 1 mg/kg provided recoveries of 81-104% with RSDs of 1.2-4.9% (n=6). Using LC-MS/MS, the method showed high sensitivity with signal-to-noise ratios>10 for concentrations below 0.002 mg/kg. HTpSPE of one sample was done in a few minutes, while numerous samples were cleaned in parallel at minimal costs with very low sample and solvent consumption. PMID:22981507

Oellig, Claudia; Schwack, Wolfgang

2012-10-19

143

Identification of odorants in frankincense (Boswellia sacra Flueck.) by aroma extract dilution analysis and two-dimensional gas chromatography-mass spectrometry/olfactometry.  

PubMed

Frankincense has been known, traded and used throughout the ages for its exceptional aroma properties, and is still commonly used in both secular and religious settings to convey a pleasant odor. Surprisingly, the odoriferous principle(s) underlying its unique odor profile have never been published. In this study, resin samples of Boswellia sacra Flueck. from both Somalia and Oman were investigated by aroma extract dilution analysis. In a comprehensive, odor-activity guided approach both chemo-analytical and human-sensory parameters were used to identify odor active constituents of the volatile fraction of B. sacra. Among the key odorants found were ?-pinene, ?-myrcene, linalool, p-cresol and two unidentified sesquiterpenoids. Overall, a total of 23 odorants were detected and analyzed by gas chromatography-olfactometry and heart-cut two-dimensional gas chromatography-mass spectrometry/olfactometry. The majority of the identified odorant compounds were oxygenated monoterpenes, along with some relevant mono- and sesquiterpenes and only one diterpenoid substance. Several of these compounds were reported here for the first time as odorous constituents in B. sacra. Identifying bioactive compounds might support a better understanding with regard to the potential benefits of frankincense, for example in aromatherapy or ecclesial settings. PMID:25468535

Niebler, Johannes; Buettner, Andrea

2015-01-01

144

Evaluation of the Impact of Sulfobutylether7 -?-Cyclodextrin on the Liquid Chromatography-Mass spectrometry Analysis of Biological Samples Arising from In Vivo Pharmacokinetic Studies.  

PubMed

The utility of cyclodextrin (CD) complexation in improving apparent solubility of drugs in parenteral formulations is well established. Administration of these formulations delivers CD directly into the systemic circulation, and it may be necessary to demonstrate unaltered in vivo disposition of a drug coadministered with a CD. Crucial to the undertaking of such a study is the need for bioanalytical assays in which CD presence does not impact drug quantitation. This is of particular importance when assessing the potential impact of in vivo CD complexation on the urinary excretion of a drug, as CDs are predominantly eliminated via glomerular filtration, and hence are present in urine at significantly higher concentration than would be present in blood and plasma. Of 23 publications (in the past 30 years) describing preclinical and clinical assessment of drug pharmacokinetics after i.v. administration of CD-enabled formulations, only two reports clearly stated that the presence of CD had no impact on assay performance. In this work, we describe the simple process involved in (1) predicting the maximum concentrations of a modified CD, sulfobutylether7 -?-CD (SBE7 -?-CD), in plasma and urine samples from preclinical studies, and (2) evaluating the impact of SBE7 -?-CD on the quantitative liquid chromatography-mass spectrometry analysis of rimantadine. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 104:1561-1562, 2015. PMID:25583633

Leong, Nathania J; Prankerd, Richard J; Shackleford, David M; Mcintosh, Michelle P

2015-04-01

145

Analysis of trace levels of sulfonamide and tetracycline antimicrobials in groundwater and surface water using solid-phase extraction and liquid chromatography/mass spectrometry  

USGS Publications Warehouse

A method has been developed for the trace analysis of two classes of antimicrobials consisting of six sulfonamides (SAs) and five tetracyclines (TCs), which commonly are used for veterinary purposes and agricultural feed additives and are suspected to leach into ground and surface water. The method used solid-phase extraction and liquid chromatography/mass spectrometry (LC/MS) with positive ion electrospray. The unique combination of a metal chelation agent (Na2EDTA) with a macroporous copolymer resulted in quantitative recoveries by solid-phase extraction (mean recovery, 98 ?? 12%) at submicrogram-per-liter concentrations. An ammonium formate/formic acid buffer with a methanol/water gradient was used to separate the antimicrobials and to optimize the signal intensity. Mass spectral fragmentation and ionization characteristics were determined for each class of compounds for unequivocal identification. For all SAs, a characteristic m/z 156 ion representing the sulfanilyl fragment was identified. TCs exhibited neutral losses of 17 amu resulting from the loss of ammonia and 35 amu from the subsequent loss of water. Unusual matrix effects were seen only for TCs in this first survey of groundwater and surface water samples from sites around the United States, requiring that TCs be quantitated using the method of standard additions.

Lindsey, M.E.; Meyer, M.; Thurman, E.M.

2001-01-01

146

Study of solvent sublation for concentration of trace phthalate esters in plastic beverage packaging and analysis by gas chromatography-mass spectrometry.  

PubMed

A novel trace analytical method based on solvent sublation (SS) and gas chromatography-mass spectrometry (GC-MS) was developed for the trace determination of twenty-two phthalate esters (PAEs) from plastic beverage packaging. In the solvent sublation section, the effects of solution pH, NaCl concentration, nitrogen flow rate, and sublation time on the sublation efficiency were investigated in detail, and the optimal conditions were obtained. The trace PAEs migrated from plastic beverage packaging to food simulants were separated and concentrated by solvent sublation, and then the trace target compounds in the concentrated solution were analyzed by GC-MS. According to the European Union Regulation, the food simulants including distilled water for the normal beverages and acetic acid solution (3%) for the acetic beverage of yogurt were prepared for migration tests. The trace analysis method showed good linearity, low limits of detection (LODs) of 1.6-183.5ng/L, and satisfied recoveries (67.3-113.7%). PMID:25660867

Chang, Lin; Bi, Pengyu; Li, Xiaochen; Wei, Yun

2015-06-15

147

Development of sample clean up methods for the analysis of Mycobacterium tuberculosis methyl mycocerosate biomarkers in sputum extracts by gas chromatography–mass spectrometry  

PubMed Central

A proof of principle gas chromatography–mass spectrometry method is presented, in combination with clean up assays, aiming to improve the analysis of methyl mycocerosate tuberculosis biomarkers from sputum. Methyl mycocerosates are generated from the transesterification of phthiocerol dimycocerosates (PDIMs), extracted in petroleum ether from sputum of tuberculosis suspect patients. When a high matrix background is present in the sputum extracts, the identification of the chromatographic peaks corresponding to the methyl derivatives of PDIMs analytes may be hindered by the closely eluting methyl ether of cholesterol, usually an abundant matrix constituent frequently present in sputum samples. The purification procedures involving solid phase extraction (SPE) based methods with both commercial Isolute-Florisil cartridges, and purpose designed molecularly imprinted polymeric materials (MIPs), resulted in cleaner chromatograms, while the mycocerosates are still present. The clean-up performed on solutions of PDIMs and cholesterol standards in petroleum ether show that, depending on the solvent mix and on the type of SPE used, the recovery of PDIMs is between 64 and 70%, whilst most of the cholesterol is removed from the system. When applied to petroleum ether extracts from representative sputum samples, the clean-up procedures resulted in recoveries of 36–68% for PDIMs, allowing some superior detection of the target analytes. PMID:25728371

Nicoara, Simona C.; Turner, Nicholas W.; Minnikin, David E.; Lee, Oona Y.-C.; O'Sullivan, Denise M.; McNerney, Ruth; Mutetwa, Reggie; Corbett, Liz E.; Morgan, Geraint H.

2015-01-01

148

Pyrolysis kinetic and product analysis of different microalgal biomass by distributed activation energy model and pyrolysis-gas chromatography-mass spectrometry.  

PubMed

To assess the energy potential of different microalgae, Chlorella sorokiniana and Monoraphidium were selected for studying the pyrolytic behavior at different heating rates with the analytical method of thermogravimetric analysis (TG), distributed activation energy model (DAEM) and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS). Results presented that Monoraphidium 3s35 showed superiority for pyrolysis at low heating rate. Calculated by DAEM, during the conversion rate range from 0.1 to 0.7, the activation energies of C. sorokiniana 21 were much lower than that of Monoraphidium 3s35. Both C. sorokiniana 21 and Monoraphidium 3s35 can produce certain amount (up to 20.50%) of alkane compounds, with 9-Octadecyne (C18H34) as the primary compound. Short-chain alkanes (C7-C13) with unsaturated carbon can be released in the pyrolysis at 500°C for both microalgal biomass. It was also observed that the pyrolysis of C. sorokiniana 21 released more alcohol compounds, while Monoraphidium 3s35 produced more saccharides. PMID:24835746

Yang, Xuewei; Zhang, Rui; Fu, Juan; Geng, Shu; Cheng, Jay Jiayang; Sun, Yuan

2014-07-01

149

Quantitation of total homocysteine in human plasma by derivatization to its N(O,S)-propoxycarbonyl propyl ester and gas chromatography-mass spectrometry analysis.  

PubMed

Much evidence supports the hypothesis that mild or moderate hyperhomocysteinaemia represents an important and independent risk factor for occlusive vascular diseases. Therefore, the accurate and reliable determination of total plasma homocysteine has gained major importance for risk assessment. Furthermore, it can help in the detection of folate and vitamin B12 deficiency. This has prompted us to develop a sensitive gas chromatography-mass spectrometry (GC-MS) method in order to quantify total homocysteine in human plasma. Prior to chromatography, reduced homocysteine was released from disulfide bonds by incubation with excess dithiothreitol and converted into its N(O,S)-propoxycarbonyl propyl ester by derivatization with n-propyl chloroformate. Aminoethylcysteine served as internal standard. The method proved to be highly linear over the entire concentration range examined (corresponding to 0-266 microM homocysteine) and showed intra-assay and inter-assay variation (relative standard deviations) of approximately 5 and 5-10%, respectively. External quality control by comparison with duplicate analysis performed on a HPLC-based system revealed satisfactory correlation. The newly developed GC-MS based method provides simple, reliable and fast quantification of total homocysteine and requires only inexpensive chemicals, which are easy to obtain. PMID:9291598

Sass, J O; Endres, W

1997-08-01

150

Development of sample clean up methods for the analysis of Mycobacterium tuberculosis methyl mycocerosate biomarkers in sputum extracts by gas chromatography-mass spectrometry.  

PubMed

A proof of principle gas chromatography-mass spectrometry method is presented, in combination with clean up assays, aiming to improve the analysis of methyl mycocerosate tuberculosis biomarkers from sputum. Methyl mycocerosates are generated from the transesterification of phthiocerol dimycocerosates (PDIMs), extracted in petroleum ether from sputum of tuberculosis suspect patients. When a high matrix background is present in the sputum extracts, the identification of the chromatographic peaks corresponding to the methyl derivatives of PDIMs analytes may be hindered by the closely eluting methyl ether of cholesterol, usually an abundant matrix constituent frequently present in sputum samples. The purification procedures involving solid phase extraction (SPE) based methods with both commercial Isolute-Florisil cartridges, and purpose designed molecularly imprinted polymeric materials (MIPs), resulted in cleaner chromatograms, while the mycocerosates are still present. The clean-up performed on solutions of PDIMs and cholesterol standards in petroleum ether show that, depending on the solvent mix and on the type of SPE used, the recovery of PDIMs is between 64 and 70%, whilst most of the cholesterol is removed from the system. When applied to petroleum ether extracts from representative sputum samples, the clean-up procedures resulted in recoveries of 36-68% for PDIMs, allowing some superior detection of the target analytes. PMID:25728371

Nicoara, Simona C; Turner, Nicholas W; Minnikin, David E; Lee, Oona Y-C; O'Sullivan, Denise M; McNerney, Ruth; Mutetwa, Reggie; Corbett, Liz E; Morgan, Geraint H

2015-04-01

151

Novel biomarkers of 3-chloro-1,2-propanediol exposure by ultra performance liquid chromatography/mass spectrometry based metabonomic analysis of rat urine.  

PubMed

To select early, sensitive biomarkers of 3-chloro-1,2-propanediol (3-MCPD) exposure, a single dose of 30 mg/kg/day 3-MCPD was administered to male Wistar rats for 40 days. Significant elevations of serum creatinine and blood urea nitrogen concentrations were observed on day 40, and urine N-acetyl-beta-D-glucosaminidase and beta-galactosidase (beta-Gal) activities were observed on day 20. Slight renal tubule hydropic degeneration and spermatozoa decreases were observed on day 10. The endogenous metabolite profile of rat urine was investigated by ultra performance liquid chromatography/mass spectrometry with electrospray ionization (ESI). Principal component analysis and partial least-squares enabled clusters to be visualized, with a trend of clustering on day 10 in ESI- and the greatest differences on days 30 and 40. Galactosylglycerol, a marker contributing to the clusters, which had earlier variations than conventional biomarkers and the most significant elevations as compared to other novel biomarkers, was first considered to be an early, sensitive biomarker in evaluating the effect of 3-MCPD exposure. The identification of galactosylglycerol was carried out by beta-Gal catalysis, and the possible mechanism of urine galactosylglycerol variation was elucidated. PMID:20158273

Li, Ying; Liu, Shuang; Wang, Cheng; Li, Kang; Shan, Yu-Juan; Wang, Xi-Jun; Sun, Chang-Hao

2010-06-21

152

Metabolomic analysis of the toxic effects of chronic exposure to low-level dichlorvos on rats using ultra-performance liquid chromatography-mass spectrometry.  

PubMed

The purpose of the current study was to assess the effects of long-term exposure to low levels of DDVP on the biochemical parameters and metabolic profiles of rats. Three different doses (2.4, 7.2, and 21.6 mg/kg body weight/day) of DDVP were administered to rats through their drinking water over 24 weeks. Significant changes in blood cholinesterase, creatinine, urea nitrogen, aspartate aminotransferase, alanine aminotransferase, and albumin concentrations were observed in the middle and high dose groups. Changes in the concentration of some urine metabolites were detected via ultra performance liquid chromatography-mass spectrometry (UPLC-MS). Dimethyl phosphate (DMP), which was exclusively detected in the treated groups, can be an early, sensitive biomarker for DDVP exposure. Moreover, DDVP treatment resulted in an increase in the lactobionic acid, estrone sulfate, and indoxyl sulfic concentrations, and a decrease in citric acid, suberic acid, gulonic acid, urea, creatinine, and uric acid. These results suggest that chronic exposure to low-level DDVP can cause a disturbance in carbohydrate and fatty acid metabolism, the antioxidant system, etc. Therefore, an analysis of the metabolic profiles can contribute to the understanding of the adverse effects of long-term exposure to low doses of DDVP. PMID:21889581

Yang, Jindan; Sun, Xiaowei; Feng, Zhijing; Hao, Dongfang; Wang, Maoqing; Zhao, Xiujuan; Sun, Changhao

2011-10-30

153

Rapid analysis of Fructus forsythiae essential oil by ionic liquids-assisted microwave distillation coupled with headspace single-drop microextraction followed by gas chromatography-mass spectrometry.  

PubMed

A rapid, green and effective miniaturized sample preparation and analytical technique, i.e. ionic liquids-assisted microwave distillation coupled with headspace single-drop microextraction (ILAMD-HS-SDME) followed by gas chromatography-mass spectrometry (GC-MS) was developed for the analysis of essential oil (EO) in Fructus forsythiae. In this work, ionic liquids (ILs) were not only used as the absorption medium of microwave irradiation but also as the destruction agent of plant cell walls. 1-Ethyl-3-methylimidazolium acetate ([C2mim]OAc) was chosen as the optimal ILs. Moreover, n-heptadecane (2.0 ?L) was selected as the appropriate suspended solvent for the extraction and concentration of EO. Extraction conditions of the proposed method were optimized using the relative peak area of EO constituents as the index, and the optimal operational parameters were obtained as follows: irradiation power (300 W), sample mass (0.7 g), mass ratio of ILs to sample (2.4), temperature (78°C) and time (3.4 min). In comparison to previous reports, the proposed method was faster and required smaller sample amount but could equally monitor all EO constituents with no significant differences. PMID:24267075

Jiao, Jiao; Ma, Dan-Hui; Gai, Qing-Yan; Wang, Wei; Luo, Meng; Fu, Yu-Jie; Ma, Wei

2013-12-01

154

Simultaneous analysis of phthalates, adipate and polycyclic aromatic hydrocarbons in edible oils using isotope dilution-gas chromatography-mass spectrometry.  

PubMed

A method for simultaneous determination of 12 priority phthalates, adipate and polycyclic aromatic hydrocarbons (PAHs) in edible oils by isotope dilution-gas chromatography-mass spectrometry (ID-GC-MS) was developed for fast, accurate and trace analysis. The extraction and clean-up procedures were optimised, and using stable isotope-labelled internal standards for each analyte, relative standard deviations (RSDs) of 0.92-10.6% and spiked sample recoveries of 80.6-97.8% were obtained. Limits of detection for PAHs were in the range of 0.15-0.77 µg/kg and those for phthalates were in the range of 4.6-10.0 µg/kg. The calibration curves exhibited good linearities with regression coefficients of R(2) ? 0.99. Twelve edible oils were examined to evaluate the efficiency of this method. Among the 12 analytes, dibutyl phthalates (DBP), diethylhexyl phthalates (DEHP), diethylhexyl adipate (DEHA), benzo[a]anthracene (B[a]A), chrysene (Chry) and benzo[b]fluoranthene (B[b]F) were detected in the range of 1.17-806 µg/kg. PMID:25029399

Oh, Min-Seok; Lee, Seon-Hwa; Moon, Myeong Hee; Lee, Dong Soo; Park, Hyun-Mee

2014-01-01

155

Supported liquid membrane-liquid chromatography-mass spectrometry analysis of cyanobacterial toxins in fresh water systems  

NASA Astrophysics Data System (ADS)

Harmful algal blooms (HABs) are increasingly becoming of great concern to water resources worldwide due to indiscriminate waste disposal habits resulting in water pollution and eutrophication. When cyanobacterial cells lyse (burst) they release toxins called microcystins (MCs) that are well known for their hepatotoxicity (causing liver damage) and have been found in eutrophic lakes, rivers, wastewater ponds and other water reservoirs. Prolonged exposure to low concentrated MCs are equally of health importance as they are known to be bioaccumulative and even at such low concentration do exhibit toxic effects to aquatic animals, wildlife and human liver cells. The application of common treatment processes for drinking water sourced from HABs infested reservoirs have the potential to cause algal cell lyses releasing low to higher amounts of MCs in finished water. Trace microcystins in water/tissue can be analyzed and quantified using Liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) following solid-phase extraction (SPE) sample clean-up procedures. However, extracting MCs from algal samples which are rich in chlorophyll pigments and other organic matrices the SPE method suffers a number of drawbacks, including cartridge clogging, long procedural steps and use of larger volumes of extraction solvents. We applied a supported liquid membrane (SLM) based technique as an alternative sample clean-up method for LC-ESI-MS analysis of MCs from both water and algal cells. Four (4) MC variants (MC-RR, -YR, -LR and -WR) from lyophilized cells of Microcystis aeruginosa and water collected from a wastewater pond were identified) and quantified using LC-ESI-MS following a SLM extraction and liquid partitioning step, however, MC-WR was not detected from water extracts. Within 45 min of SLM extraction all studied MCs were extracted and pre-concentrated in approximately 15 ?L of an acceptor phase at an optimal pH 2.02 of the donor phase (sample). The highest total quantifiable intracellular and extracellular MCs were 37.039 ± 0.087 ?g/g DW and 5.123 ± 0.018 ?g/L, respectively. The concentrations of MC-RR were the highest from all samples studied recording maximum values of 21.579 ± 0.066 ?g/g DW and 3.199 ± 0.012 ?g/L for intracellular and extracellular quantities, respectively.

Mbukwa, Elbert A.; Msagati, Titus A. M.; Mamba, Bhekie B.

156

Liquid chromatography\\/mass spectrometry-based structural analysis of new platycoside metabolites transformed by human intestinal bacteria  

Microsoft Academic Search

Platycosides, the main active constituents of Platycodi Radix, have been thoroughly studied for the characterization of their potent biological activities. However, metabolism of platycosides has not yet been characterized. A HPLC electrospray ionization-tandem mass spectrometry (LC\\/ESI-MSn) approach was applied to new complex platycoside metabolites transformed by human intestinal bacteria to identify their structures and determine metabolic pathway. The molecular weights

Young Wan Ha; Yun-Cheol Na; In Jin Ha; Dong-Hyun Kim; Yeong Shik Kim

2010-01-01

157

Direct pharmacokinetic analysis of puqietinone by in vivo microdialysis sampling and turbulent-flow chromatography coupled with liquid chromatography-mass spectrometry.  

PubMed

Sample pretreatment is a key step in bioanalytical process because of possible interference and matrix effects in mass spectrometry analysis. In this work, a novel strategy towards high speed and sensitivity was developed combining in vivo microdialysis (MD) sampling, turbulent-flow chromatography (TFC), and liquid chromatography-mass spectrometry (LC-MS). The procedures of cleanup, preconcentration, and separation were completed on-line in one step within 10min. During the MD optimization procedure, 1% hydroxypropyl-?-cyclodextrin (HP-?-CD) was used to improve the relative recovery of the analyte. Untreated MD samples were directly injected, and a TFC precolumn was flushed for 1min with aqueous phase of 4mL/min flow rate to desalt and concentrate biosamples. The retained analytes were then back-flushed by a switching valve onto a fast LC column (4.6mm×50mm, 1.8?m) for separation. Another diverter valve was employed to prevent the HP-?-CD that interferes with the ESI process from entering the MS. Puqietinone, a lipophilic alkaloid from Fritillaria puqiensis, was used as a case for validation. Results showed that the limit of quantification for puqietinone was 0.10ng/mL, and good linearity (R(2)=0.9993) was maintained over the range of 1.02-200.02ng/mL. Accuracy and precision were satisfactory within the range of the standard curve. This approach was able to effectively eliminate the influences of matrix effect and carry-over as the injection volume increased up to 20?L. The developed method was successfully applied to pharmacokinetic study of puqietinone after intravenous administration to rat. Results demonstrate the potential of using MD with TFC-LC/MS for in vivo monitoring experiments. PMID:22658466

Xin, Gui-Zhong; Cao, Liu; Shi, Zi-Qi; Li, Hui-Jun; Wen, Xiao-Dong; Chen, Jun; Qi, Lian-Wen; Li, Ping

2012-06-15

158

Identification of polychlorinated styrene compounds in heron tissues by gas-liquid chromatography-mass spectrometry  

USGS Publications Warehouse

Unknown compounds detected in Ardea herodias tissues are identified by gas-liquid chromatography-mass spectrometry as residues of octachlorostyrene. Heptachlorostyrene and hexachlorostyrene were tentatively identified.

Reichel, W.L.; Prouty, R.M.; Gay, M.L.

1977-01-01

159

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

PubMed

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

Barron, Leon; Gilchrist, Elizabeth

2014-01-01

160

Evaluation of the QuEChERS Method and Gas Chromatography–Mass Spectrometry for the Analysis Pesticide Residues in Water and Sediment  

PubMed Central

A method for the determination of pesticide residues in water and sediment was developed using the QuEChERS method followed by gas chromatographymass spectrometry. The method was validated in terms of accuracy, specificity, linearity, detection and quantification limits. The recovery percentages obtained for the pesticides in water at different concentrations ranged from 63 to 116%, with relative standard deviations below 12%. The corresponding results from the sediment ranged from 48 to 115% with relative standard deviations below 16%. The limits of detection for the pesticides in water and sediment were below 0.003 mg L?1 and 0.02 mg kg?1, respectively. PMID:21165598

de Macedo, A. N.; Vicente, G. H. L.; Nogueira, A. R. A.

2010-01-01

161

Serum fatty acid profiles and potential biomarkers of ankylosing spondylitis determined by gas chromatography-mass spectrometry and multivariate statistical analysis.  

PubMed

Ankylosing spondylitis (AS) is a common chronic inflammatory rheumatic disease. Early and accurate detection is essential for effective disease treatment. Recently, research has focused on genomics and proteomics. However, the associated metabolic variations, especially fatty acid profiles, have been poorly discussed. In this study, the gas chromatography-mass spectrometry (GC-MS) approach and multivariate statistical analysis were used to investigate the metabolic profiles of serum free fatty acids (FFAs) and esterified fatty acids (EFAs) in AS patients. The results showed that significant differences in most of the FFA (C12:0, C16:0, C16:1, C18:3, C20:4, C20:5, C22:5 and C22:6) and EFA (C12:0, C16:1, C18:0, C18:1, C18:2, C18:3, C20:4 and C22:6) concentrations were found between the AS patients and healthy controls (p?analysis and partial least squares discriminant analysis were performed to classify the AS patients and controls. Additionally, FFAs C20:4, C12:0, C18:3 and EFAs C22:6, C12:0 were confirmed as potential biomarkers to identify AS patients and healthy controls. The present study highlights that differences in the serum FFA and EFA profiles of AS patients reflect the metabolic disorder. Moreover, FFA and EFA biomarkers appear to have clinical applications for the screening and diagnosis of AS. Copyright © 2014 John Wiley & Sons, Ltd. PMID:25223299

Chen, Rui; Han, Su; Dong, Daming; Wang, Yansong; Liu, Qingpeng; Xie, Wei; Li, Mi; Yao, Meng

2015-04-01

162

Methods of Analysis - Determination of Pyrethroid Insecticides in Water and Sediment Using Gas Chromatography/Mass Spectrometry  

USGS Publications Warehouse

A method for the determination of 14 pyrethroid insecticides in environmental water and sediment samples is described. The method was developed by the U.S. Geological Survey in response to increasing concern over the effects of pyrethroids on aquatic organisms. The pyrethroids included in this method are ones that are applied to many agricultural and urban areas. Filtered water samples are extracted for pyrethroids using solid-phase extraction (SPE) with no additional cleanup steps. Sediment and soil samples are extracted using a microwave-assisted extraction system, and the pyrethroids of interest are separated from co-extracted matrix interferences by passing the extracts through stacked graphitized carbon and alumina SPE cartridges, along with the use of high-performance liquid chromatography and gel-permeation chromatography (HPLC/GPC). Quantification of the pyrethroids from the extracted water and sediment samples is done using gas chromatography with mass spectrometry (GC/MS) or gas chromatography with tandem mass spectrometry (GC/MS/MS). Recoveries in test water samples fortified at 10 ng/L ranged from 83 to 107 percent, and recoveries in test sediment samples fortified at 10 ug/kg ranged from 82 to 101 percent; relative standard deviations ranged from 5 to 9 percent in the water samples and 3 to 9 percent in the sediment samples. Method detection limits (MDLs), calculated using U.S. Environmental Protection Agency procedures (40 CFR 136, Appendix B), in water ranged from 2.0 to 6.0 ng/L using GC/MS and 0.5 to 1.0 ng/L using GC/MS/MS. For sediment, the MDLs ranged from 1.0 to 2.6 ug/kg dry weight using GC/MS and 0.2 to 0.5 ug/kg dry weight using GC/MS/MS. The matrix-spike recoveries for each compound, when averaged for 12 environmental water samples, ranged from 84 to 96 percent, and when averaged for 27 environmental sediment samples, ranged from 88 to 100 percent.

Hladik, Michelle L.; Smalling, Kelly L.; Kuivila, Kathryn M.

2009-01-01

163

Hydrocarbons and fuels analyses with the supersonic gas chromatography mass spectrometry--the novel concept of isomer abundance analysis.  

PubMed

Hydrocarbon analysis with standard GC-MS is confronted by the limited range of volatile compounds amenable for analysis and by the similarity of electron ionization mass spectra for many compounds which show weak or no molecular ions for heavy hydrocarbons. The use of GC-MS with supersonic molecular beams (Supersonic GC-MS) significantly extends the range of heavy hydrocarbons that can be analyzed, and provides trustworthy enhanced molecular ion to all hydrocarbons. In addition, unique isomer mass spectral features are obtained in the ionization of vibrationally cold hydrocarbons. The availability of molecular ions for all hydrocarbons results in the ability to obtain unique chromatographic isomer distribution patterns that can serve as a new method for fuel characterization and identification. Examples of the applicability and use of this novel isomer abundance analysis (IAA) method to diesel fuel, kerosene and oil analyses are shown. It is suggested that in similarity to the "three ions method" for identification purposes, three isomer abundance patterns can serve for fuel characterization. The applications of the Supersonic GC-MS for engine motor oil analysis and transformer oil analysis are also demonstrated and discussed, including the capability to achieve fast 1-2s sampling without separation for oil and fuel fingerprinting. The relatively fast analysis of biodiesel is described, demonstrating the provision of molecular ions to heavy triglycerides. Isomer abundance analysis with the Supersonic GC-MS could find broad range of applications including petrochemicals and fuel analysis, arson analysis, environmental oil/fuel spill analysis, fuel adulteration analysis and motor oil analysis. PMID:18495139

Fialkov, Alexander B; Gordin, Alexander; Amirav, Aviv

2008-06-27

164

[Analysis of fatty acids in Gmnocypris przewalskii oil by gas chromatography/mass spectrometry with base-catalyzed transesterification].  

PubMed

The composition of fatty acids (FA) in Gymnocypris przewalskii oil was identified and quantified by gas chromatography (GC)/electron impact (EI) mass spectrometry (MS). A base-catalyzed transesterification method was used to convert fatty acids to methyl esters. The lipids were extracted using petroleum ether and the total lipids in dried meat and skin of Gymnocypris przewalskii were about 25%. Forty-seven fatty acids were identified in the current study. Main types of fatty acids found in the oils were normal saturated, mono-branched, multi-branched, cyclopropane, furanoid, normal monounsaturated and polyunsaturated fatty acids. Saturated fatty acids were approximately 25. 7% of the total, and the main components were C(14:0) (3.4%), C(16:0) (19.4%) and C(18:0) (1.1%). Unsaturated fatty acids were totally 73.6%, and the major components of monounsaturated fatty acids were C(16:1 (9)) (19.8%), C(18:1) (9)) (18. 6%) and C(18:1 (11)) (7.3%); polyunsaturated fatty acids were mainly composed of C(18:2 (9,12)) (4.8%), C(18:3 (9, 12, 15)) (3.1%), C(20:4 (5, 8, 1, 14)) (1.2%), C(20:5 (5, 8, 11, 14, 17)) (EPA, 9.4%) and C(22:6 (4, 7, 10, 13, 16, 19)) (DHA, 6.7%). Especially, furyl-, cyclopropane- and several odd and branched chain fatty acids were found in Gymnocypris przewalskii oil. It is thus an important dietary resource of functional fatty acids. PMID:16830471

Bo, Haibo; Wang, Xia; Zhai, Zongde; Li, Yongmin; Chen, Liren

2006-03-01

165

Application of dissimilarity indices, principal coordinates analysis, and rank tests to peak tables in metabolomics of the gas chromatography/mass spectrometry of human sweat.  

PubMed

The majority of works in metabolomics employ approaches based on principal components analysis (PCA) and partial least-squares, primarily to determine whether samples fall within large groups. However, analytical chemists rarely tackle the problem of individual fingerprinting, and in order to do this effectively, it is necessary to study a large number of small groups rather than a small number of large groups and different approaches are required, as described in this paper. Furthermore, many metabolomic studies on mammals and humans involve analyzing compounds (or peaks) that are present in only a certain portion of samples, and conventional approaches of PCA do not cope well with sparse matrices where there may be many 0s. There is, however, a large number of qualitative similarity measures available for this purpose that can be exploited via principal coordinates analysis (PCO). It can be shown that PCA scores are a specific case of PCO scores, using a quantitative similarity measure. A large-scale study of human sweat consisting of nearly 1000 gas chromatography/mass spectrometry analyses from the sweat of an isolated population of 200 individuals in Carinthia (Southern Austria) sampled once per fortnight over 10 weeks was employed in this study and grouped into families. The first step was to produce a peak table requiring peak detection, alignment, and integration. Peaks were reduced from 5080 to 373 that occurred in at least 1 individual over 4 out of 5 fortnights. Both qualitative (presence/absence) and quantitative (equivalent to PCA) similarity measures can be computed. PCO and the Kolomorogov-Smirnoff (KS) rank test are applied to these similarity matrices. It is shown that for this data set there is a reproducible individual fingerprint, which is best represented using the qualitative similarity measure as assessed both by the Hotelling t2 statistic as applied to PCO scores and the probabilities associated with the KS rank test. PMID:17602669

Xu, Yun; Gong, Fan; Dixon, Sarah J; Brereton, Richard G; Soini, Helena A; Novotny, Milos V; Oberzaucher, Elisabeth; Grammer, Karl; Penn, Dustin J

2007-08-01

166

Analysis of fatty acids in lung tissues using gas chromatography-mass spectrometry preceded by derivatization-solid-phase microextraction with a novel fiber.  

PubMed

In this article, a laboratory-made sol-gel derived fiber with butyl methacrylate/hydroxy-terminated silicone oil (BMA/OH-TSO) coating was first used for headspace solid-phase microextraction (HS-SPME) of medium and long chain fatty acids after derivatization and applied to the analysis of fatty acids in lung tissues by coupling to gas chromatography-mass spectrometry (GC-MS). The experimental parameters for derivatization, HS-SPME and desorption were optimized. Fatty acids in cancerous lung tissues from five patients with lung cancer were determined under the optimized conditions. Normal lung tissues from the same five patients were used as controls. This fiber showed higher extraction efficiency for fatty acids after derivatization when compared with commercial polydimethylsiloxane (PDMS) and polydimethylsiloxane-divinylbenzene (PDMS/DVB) fibers due to the three-dimensional network in the coating. The method presented in this paper showed satisfactory precision, accuracy, linearity and limits of detection (LODs). The relative standard deviation values were below 13.3% (n=5) and the recoveries obtained ranged from 76.35% to 107.0%. The results obtained using the SPME method were also compared with those got by using liquid-liquid extraction (LLE) technique. It was found that the sensitivity could be enhanced by the SPME method. The analysis of the cancerous lung tissues and normal controls from five patients with lung cancer indicated that the main components of lung tissue were palmitic acid (C16:0), stearic acid (C18:0) and lignoceric acid (C24:0). A comparison between the levels of the fatty acids in cancerous lung tissues and normal controls from the same a patient with lung cancer shows that most of the saturated fatty acids showed higher levels in cancerous lung tissues, while unsaturated fatty acids showed higher levels in normal controls on the whole. PMID:17723460

Cha, Dongmei; Liu, Mingming; Zeng, Zhaorui; Cheng, Dong'e; Zhan, Guoqing

2006-07-14

167

The toxicity of 3-chloropropane-1,2-dipalmitate in Wistar rats and a metabonomics analysis of rat urine by ultra-performance liquid chromatography-mass spectrometry.  

PubMed

3-Monochloropropane-1,2-diol(3-MCPD) fatty acid esters can release free 3-MCPD in a certain condition. Free 3-MCPD is a well-known food contaminant and is toxicological well characterized, however, in contrast to free 3-MCPD, the toxicological characterization of 3-MCPD fatty acid esters is puzzling. In this study, toxicological and metabonomics studies of 3-chloropropane-1,2-dipalmitate(3-MCPD dipalmitate) were carried out based on an acute oral toxicity test, a 90-day feeding test and ultra-performance liquid chromatography-mass spectrometry (UPLC-MS) analysis. The LD50 value of 3-MCPD dipalmitate was determined to be 1780 mg/kg body weight (bw) for Wistar rats. The results of the 90-day feeding test in male Wistar rats showed that 3-MCPD dipalmitate caused a significant increase in blood urea nitrogen and creatinine in the high-dose group (267 mg/kg bw/day) compared to control rats. Renal tubular epithelium cell degeneration and renal tubular hyaline cast accumulation were the major histopathological changes in rats administered 3-MCPD dipalmitate. Urine samples obtained after the 90-day feeding test and analyzed by UPLC-MS showed that the differences in metabolic profiles between control and treated rats were clearly distinguished by partial least squares-discriminant analysis (PLS-DA) of the chromatographic data. Five metabolite biomarkers which had earlier and significant variations had been identified, they were first considered to be the early, sensitive biomarkers in evaluating the effect of 3-MCPD dipalmitate exposure, and the possible mechanism of these biomarkers variation was elucidated. The combination of histopathological examination, clinical chemistry and metabolomics analyses in rats resulted in a systematic and comprehensive assessment of the long-term toxicity of 3-MCPD dipalmitate. PMID:24140137

Li, Jianshuang; Wang, Sen; Wang, Maoqing; Shi, Wenxiu; Du, Xiaoyan; Sun, Changhao

2013-11-25

168

Rapid structural analysis of the in vitro and in vivo metabolism of SK & F 95448 by the combined use of thermospray liquid chromatography/mass spectrometry and liquid chromatography/tandem mass spectrometry.  

PubMed

The thermospray liquid chromatography/mass spectrometry (LC/MS) interface has had a major impact on the direct analysis of the metabolic fate of xenobiotics in complex biological media. This paper outlines the rapidity and power of the LC/MS approach, and shows how detailed structural information can be obtained without recourse to individual compound isolation. This provides a great saving in time and effort. The additional specificity of liquid chromatography/tandem mass spectrometry is highlighted in identifying the sites of metabolic transformation. The ability to handle biological samples with little or no clean-up using wide high-performance liquid chromatographic gradients is a key feature of the success of this methodology. PMID:2553171

Blake, T J; Beattie, I G

1989-08-01

169

Determination of cellular redox status by stable isotope dilution liquid chromatography/mass spectrometry analysis of glutathione and glutathione disulfide.  

PubMed

Oxidation of glutathione (GSH) to glutathione disulfide (GSSG) occurs during cellular oxidative stress. The redox potential of the 2GSH/GSSG couple, which is determined by the Nernst equation, provides a means to assess cellular redox status. It is difficult to accurately quantify GSH and GSSG due to the ease with which GSH is oxidized to GSSG during sample preparation. To overcome this problem, a stable isotope dilution liquid chromatography/multiple reaction monitoring mass spectrometry (LC/MRM-MS) method has been developed using 4-fluoro-7-sulfamoylbenzofurazan (ABD-F) derivatization. ABD-F derivatization of the GSH thiol group was rapid, quantitative, and occurred at room temperature. The LC/MRM-MS method, which requires no sample clean-up, was validated within the calibration ranges of 5 to 400 nmol/mL in cell lysates for GSH and 0.5 to 40 nmol/mL in cell lysates for GSSG. Calibration curves prepared by adding known concentrations of GSH and GSSG to cell lysates were parallel to the standard curve prepared in buffers. GSH and GSSG concentrations were determined in two monocyte/macrophage RAW 267.4 cell lines with or without 15-LOX-1 expression (R15LO and RMock cells, respectively) after treatment with the bifunctional electrophile 4-oxo-2(E)-nonenal (ONE). R15LO cells synthesized much higher concentrations of the lipid hydroperoxide, 15(S)-hydroperoxyeicosatetraenoic acid (15-HPETE), which undergoes homolytic decomposition to ONE. GSH was depleted by ONE treatment in both RMock and R15LO cells, leading to significant increases in their redox potentials. However, R15LO cells had higher GSH concentrations (most likely through increased GSH biosynthesis) and had increased resistance to ONE-mediated GSH depletion than RMock cells. Consequently, R15LO cells had lower reduction potentials at all concentrations of ONE. GSSG concentrations were higher in R15LO cells after ONE treatment when compared with the ONE-treated RMock cells. This suggests that increased expression of 15(S)-HPETE modulates the activity of cellular GSH reductases or the transporters involved in removal of GSSG. PMID:18215009

Zhu, Peijuan; Oe, Tomoyuki; Blair, Ian A

2008-01-01

170

Estimation of brassylic acid by gas chromatography-mass spectrometry  

SciTech Connect

The main focus of this work is to estimate Brassylic Acid (BA) using gas chromatography-mass spectrometry (GC-MS). BA is a product obtained from the oxidative cleavage of Erucic Acid (EA). BA has various applications for making nylons and high performance polymers. BA is a 13 carbon compound with two carboxylic acid functional groups at the terminal end. BA has a long hydrocarbon chain that makes the molecule less sensitive to some of the characterization techniques. Although BA can be characterized by NMR, both the starting material (EA) and products BA and nonanoic acid (NA) have peaks at similar {delta}, ppm values. Hence it becomes difficult for the quick estimation of BA during its synthesis.

Mohammed J. Nasrullah, Erica N. Pfarr, Pooja Thapliyal, Nicholas S. Dusek, Kristofer L. Schiele, Christy Gallagher-Lein, and James A. Bahr

2010-10-29

171

Precolumn sample-enrichment device for analysis of ambient volatile organics by gas chromatography-mass spectrometry  

SciTech Connect

Gas chromatographic-mass spectrometric (GC/MS) identification of air pollutants generally requires a preconcentration step to provide sufficient sample for analysis. Cryogenic trapping is often used to enrich the sample since nitrogen and oxygen are not condensed. It does, however, concentrate enormous quantities of water and carbon dioxide - enough to plug high-resolution narrow-bore capillary columns needed for separation of complex environmental samples. Whole-air samples were collected in stainless steel containers or Tedlar bags for analysis by gas chromatography with flame ionization detection (GC/FID). In order to provide identification of unknown peaks and confirmation of tentatively named peaks, the system described herein was designed and built to enrich samples for GC/MS analysis of volatile organics. The preconcentration system consists of a solid sorbent trap and a cryogenic trap used in sequence to collect organic vapors and focus them for analysis by GC/MS.

Arnts, R.R.

1985-01-01

172

EVALUATION OF PARTICLE BEAM LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY FOR THE ANALYSIS OF POLAR SEMIVOLATILE ORGANIC COMPOUNDS IN AIR SAMPLES  

EPA Science Inventory

This report describes the initial evaluation of a particle beam liquid chromatograph/mass spectrometer for the analysis of polar semivolatile organic compounds in air samples. This study was concentrated on examining and optimizing instrumental operating parameters, evaluating th...

173

Hydrocarbons and fuels analyses with the supersonic gas chromatography mass spectrometry—The novel concept of isomer abundance analysis  

Microsoft Academic Search

Hydrocarbon analysis with standard GC–MS is confronted by the limited range of volatile compounds amenable for analysis and by the similarity of electron ionization mass spectra for many compounds which show weak or no molecular ions for heavy hydrocarbons. The use of GC–MS with supersonic molecular beams (Supersonic GC–MS) significantly extends the range of heavy hydrocarbons that can be analyzed,

Alexander B. Fialkov; Alexander Gordin; Aviv Amirav

2008-01-01

174

Molecularly imprinted solid phase extraction of urinary diethyl thiophosphate and diethyl dithiophosphate and their analysis by gas chromatography-mass spectrometry.  

PubMed

An analytical method involving molecularly imprinted solid phase extraction (MISPE) and gas chromatography-mass spectrometry (GC-MS) was developed for the analysis of organophosphates metabolites (diethyl thiophosphate--DETP and diethyl dithiophosphate - DEDTP) in human urine samples. A DETP molecularly imprinted polymer (MIP) was synthesized using 4-vinylpiridine as the functional monomer and ethylene glycol dimethacrylate as the cross-linker. The conditioning step of the MISPE was conducted by running 3 mL of acetonitrile, 3 mL of 0.1 mol L?¹ dibasic phosphate buffer at pH 11 and 2 mL of water through the molecularly imprinted polymer (MIP) cartridge. The extraction step was executed using 1.0 mL of a urine sample, with the pH previously adjusted to 3.0. Finally, the analytes were eluted with 3 mL of acetonitrile and derivatized with 3% 2,3,4,5,6-pentafluorobenzyl bromide solution at room temperature for 1h. The sample was analyzed by GC-MS in the SIM (selected ion monitoring) mode. Analytical calibration curves for DETP and DEDTP were constructed using a pool of urine samples and six levels of concentration. The method was found to be linear from 10 to 500 ?g L?¹ (r>0.99) with limits of quantification of 10 ?g L?¹ for both analytes. The within-day and between-day precisions were evaluated (as %RSD) and all the results were <15% for both analytes. The method was accurate (relative error<±15%), with good robustness. PMID:23153647

Santos, Mariane Gonçalves; Vitor, Ricardo Vilela; Andrade, Felipe Lopes; Martins, Isarita; Figueiredo, Eduardo Costa

2012-11-15

175

Analysis of bitter limonoids in citrus juices by atmospheric pressure chemical ionization and electrospray ionization liquid chromatography-mass spectrometry.  

PubMed

Improved analytical techniques for bitter limonoids in citrus and citrus juices can expedite the evaluation of freeze-induced citrus damage for citrus growers and juice quality for citrus juice producers. Microbore normal-phase and reverse-phase chromatography coupled to a mass spectrometer operating in a positive ion atmospheric pressure chemical ionization and electrospray ionization modes were found to be rapid, selective, and sensitive methods for the analysis of the bitter limonoids limonin and nomilin in citrus juices. Analysis was performed on a chloroform extract of citrus juice to which an internal standard was added. The methods are capable of detecting citrus limonoids in citrus juice in the 60-200 picogram range and quantifying citrus juice limonoids in concentrations as low as 120 picograms. An accurate "total limonoid bitterness" in citrus juice, as represented by the combined occurrence of limonin and nomilin, is easily determined by these methods. PMID:12797731

Manners, Gary D; Breksa, Andrew P; Schoch, Thomas K; Hidalgo, Marlene B

2003-06-18

176

Challenges in the development of bioanalytical liquid chromatography-mass spectrometry method with emphasis on fast analysis.  

PubMed

The development of bioanalytical methods has become more and more challenging over the past years due to very demanding requirements in terms of method reliability, sensitivity, speed of analysis and sample throughput. LC-MS/MS has established itself as a method of choice for routine analysis of biological materials. A development of such method consists of several steps including sample preparation and clean-up step, efficient chromatographic separation, sensitive and selective detection of analytes in complex matrices, a choice of convenient data processing and calibration approach and finally method validation. Each of these steps has its own constraints and challenges, which are discussed in detail in this review. Novel and modern approaches in sample preparation, chromatography and detection are especially emphasized. Attention is paid to proper calibration approach and matrix effects that can seriously affect method accuracy and precision. PMID:22999195

Nováková, Lucie

2013-05-31

177

Determination of boiling point of petrochemicals by gas chromatography-mass spectrometry and multivariate regression analysis of structural activity relationship.  

PubMed

Accurate understanding of analyte boiling points (BP) is of critical importance in gas chromatographic (GC) separation and crude oil refinery operation in petrochemical industries. This study reported the first combined use of GC separation and partial-least-square (PLS1) multivariate regression analysis of petrochemical structural activity relationship (SAR) for accurate BP determination of two commercially available (D3710 and MA VHP) calibration gas mix samples. The results of the BP determination using PLS1 multivariate regression were further compared with the results of traditional simulated distillation method of BP determination. The developed PLS1 regression was able to correctly predict analytes BP in D3710 and MA VHP calibration gas mix samples, with a root-mean-square-%-relative-error (RMS%RE) of 6.4%, and 10.8% respectively. In contrast, the overall RMS%RE of 32.9% and 40.4%, respectively obtained for BP determination in D3710 and MA VHP using a traditional simulated distillation method were approximately four times larger than the corresponding RMS%RE of BP prediction using MRA, demonstrating the better predictive ability of MRA. The reported method is rapid, robust, and promising, and can be potentially used routinely for fast analysis, pattern recognition, and analyte BP determination in petrochemical industries. PMID:24881546

Fakayode, Sayo O; Mitchell, Breanna S; Pollard, David A

2014-08-01

178

Multiresidue analysis of insecticides and other selected environmental contaminants in poultry manure by gas chromatography/mass spectrometry.  

PubMed

An analytical method was developed for the simultaneous determination in poultry manure of 41 organic contaminants belonging to different chemical classes: pesticides, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and polybrominated diphenyl ethers. Poultry manure was extracted with a modified QuEChERS method, and the extracts were analyzed by isotope dilution GC/MS. Recovery of these contaminants from samples spiked at levels ranging from 25 to 100 ng/g was satisfactory for all the compounds. The developed procedure provided LODs from 0.8 to 9.6 ng/g. The analysis of poultry manure samples collected on different farms confirmed the presence of some of the studied contaminants. Pyrethroids and polycyclic aromatic hydrocarbons were the main contaminants detected. DDT and its metabolite DDE were also found but at relatively low concentrations. PMID:25145126

Aznar, Ramón; Albero, Beatriz; Sánchez-Brunete, Consuelo; Miguel, Esther; Tadeo, José L

2014-01-01

179

Sample collection and preparation of biofluids and extracts for gas chromatography-mass spectrometry.  

PubMed

To maximize the utility of gas chromatography-mass spectrometry (GC-MS) in metabonomics research, all stages of the experimental design should be standardized, including sample collection, storage, preparation, and sample separation. Moreover, the prerequisite for any GC-MS analysis is that a compound must be volatile and thermally stable if it is to be analyzed using this technique. Since many metabolites are nonvolatile and polar in nature, they are not readily amenable to analysis by GC-MS and require initial chemical derivatization of the polar functional groups in order to reduce the polarity and to increase the thermal stability and volatility of the analytes. In this chapter, an overview is presented of the optimum approach to sample collection, storage, and preparation for gas chromatography-mass spectrometry-based metabonomics with particular focus on urine samples as example of biofluids. PMID:25677148

Emwas, Abdul-Hamid M; Al-Talla, Zeyad A; Kharbatia, Najeh M

2015-01-01

180

Isolation of polyketides from Prymnesium parvum (Haptophyta) and their detection by liquid chromatography/mass spectrometry metabolic fingerprint analysis.  

PubMed

Prymnesium parvum is a microalga that forms blooms coupled with the presence of potent exotoxins; however, no chemical standards are currently available for the toxins. Streamlined methods are presented for the separation and enrichment of polyketide toxins, prymnesin-1 (prym1) and prymnesin-2 (prym2). Prymnesins were separated by reversed-phase chromatography and detected by positive-mode electrospray ionization MS to generate a unique metabolic fingerprint. More than 10 ions were detected and mass assignments were in agreement with predicted isotopic distributions for the intact compounds and related fragments; ions occurred as multiply protonated species and with common salt adducts. The most prevalent ion was observed at 919.88 m/z, which represents the aglycone [prymagly+2H](2+) backbone structure common to both molecules. Expanded mass spectra for this and related ions were in excellent agreement (<0.5ppm) with empirically derived spectra based on elemental composition and naturally occurring isotopes. These investigations have confirmed the isolation of polyketide prymnesins from whole cells, which heretofore has not been reproduced since their original characterization. Moreover, this study represents the first time these compounds have been verified in aqueous materials. These tools should allow the direct identification and analysis of polyketide prymnesins, which will greatly improve our understanding of these toxins in P. parvum. PMID:23916560

Manning, Schonna R; La Claire Ii, John W

2013-11-15

181

Quantitative determination of amphetamines, cocaine, and opiates in human hair by gas chromatography\\/mass spectrometry  

Microsoft Academic Search

Hair of young subjects (N=36) suspected for drug abuse was analysed for morphine, codeine, heroin, 6-acetylmorphine, cocaine, methadone, amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA), and 3,4-methylenedioxyethylamphetamine (MDEA). The analysis of morphine, codeine, heroin, 6-acetylmorphine, cocaine, and methadone in hair included incubation in methanol, solid-phase extraction, derivatisation by the mixture of propionic acid anhydride and pyridine, and gas chromatography\\/mass spectrometry (GC\\/MS).

L Skender; V Kara?i?; I Br?i?; A Bagari?

2002-01-01

182

Characterization of sterols by gas chromatography-mass spectrometry of the trimethylsilyl ethers  

Microsoft Academic Search

The utility of combined gas chromatography-mass spectrometry in the analysis and characterization of sterols has been explored.\\u000a Methylene unit (MU) values and principal mass spectrometric data are presented for trimethylsilyl ethers of 28 sterols, including\\u000a the major natural sterols. The diagnostic value of the fragmentation of trimethylsilyl ethers of ?5-3 ?-hydroxysteroids has been confirmed. Characteristic fragmentations of ?4-3 ?-trimethylsilyloxysteroids, and

C. J. W. Brooks; E. C. Horning; J. S. Young

1968-01-01

183

Gas chromatography-mass spectrometry evidence for several endogenous auxins in pea seedling organs  

Microsoft Academic Search

Qualitative analysis by gas chromatography-mass spectrometry (GC-MS) of the auxins present in the root, cotyledons and epicotyl of 3-dold etiolated pea (Pisum sativum L., cv. Alaska) seedlings has shown that all three organs contain phenylacetic acid (PAA), 3-indoleacetic acid (IAA) and 4-chloro-3-indoleacetic acid (4Cl-IAA). In addition, 3-indolepropionic acid (IPA) was present in the root and 3-indolebutyric acid (IBA) was detected

Elnora A. Schneider; Clement W. Kazakoff; Frank Wightman

1985-01-01

184

Formation of dehydroalanine from mimosine and cysteine: artifacts in gas chromatography/mass spectrometry based metabolomics  

SciTech Connect

Trimethylsilyation is a chemical derivatization procedure routinely applied in gas chromatography-mass spectrometry (GC-MS)-based metabolomics. In this report, through de novo structural elucidation and comparison with authentic standards, we demonstrate that mimosine can be completely converted into dehydroalanine and 3,4-dihydroxypyridine during the trimethylsilyating process. Similarly, dehydroalanine can be formed from derivatization of cysteine. This conversion is a potential interference in GC-MS-based global metabolomics, as well as in analysis of amino acids.

Kim, Young-Mo; Metz, Thomas O.; Hu, Zeping; Wiedner, Susan D.; Kim, Jong Seo; Smith, Richard D.; Morgan, William F.; Zhang, Qibin

2011-08-15

185

Direct chemical-analysis of uv laser-ablation products of organic polymers by using selective ion monitoring mode in gas-chromatography mass-spectrometry  

USGS Publications Warehouse

Trace quantities of laser ablated organic polymers were analyzed by using commercial capillary column gas chromatography/mass spectrometry; the instrument was modified so that the laser ablation products could be introduced into the capillary column directly and the constituents of each peak in the chromatogram were identified by using a mass spectrometer. The present study takes advantage of the selective ion monitoring mode for significantly improving the sensitivity of the mass spectrometer as a detector, which is critical in analyzing the trace quantities and confirming the presence or absence of the species of interest in laser ablated polymers. The initial composition of the laser ablated polymers was obtained by using an electron impact reflectron time-of-flight mass spectrometer and the possible structure of the fragments observed in the spectra was proposed based on the structure of the polymers.

Choi, Y.; Lee, H.W.; Fountain, S.T.; Lubman, D.M.

1994-01-01

186

Fast analysis of principal volatile compounds in crude and processed Atractylodes macrocephala by an automated static headspace gas chromatography-mass spectrometry  

PubMed Central

Objective: Atractylodes macrocephala, a famous herbal medicine, is used extensively in the practice of Traditional Chinese Medicine (TCM). Processing procedure is a common approach that usually occurs before A. macrocephala is prescribed. This paper describes a sensitive and specific assay for the determination of principal volatile compounds in crude and processed A. macrocephala. Materials and Methods: The present study concentrated on the development of a static headspace gas chromatography-mass spectrometry (SHS-GC/MS) for separating and identifying of volatile compounds from crude and processed A. macrocephala samples. Results: The results showed that the volatile oil in crude and processed A. macrocephala was markedly quantitatively and qualitatively different. Processing resulted in the reduction of volatile oil contents and variation of chemical compositions in A. macrocephala. Conclusion: The proposed method proved that SHS-GC/MS is rapid and specific, and should also be useful for evaluating the quality of crude and processed medicinal herbs. PMID:25210311

Zhang, Jida; Cao, Gang; Xia, Yunhua; Wen, Chengping; Fan, Yongsheng

2014-01-01

187

Use of headspace sorptive extraction coupled to gas chromatography-mass spectrometry for the analysis of volatile polycyclic aromatic hydrocarbons in herbal infusions.  

PubMed

A solvent-free method is described for the determination of 10 volatile polycyclic aromatic hydrocarbons (PAHs), considered as priority pollutants by the EU, in different herbal infusions using headspace sorptive extraction (HSSE) and gas chromatography-mass spectrometry (GC-MS). The parameters affecting both the extraction and thermal desorption steps in the HSSE were optimized by means of Plackett-Burman designs. Ten millilitres of the herbal infusion was submitted to the HSSE preconcentration in the presence of salt for 4h at 88 °C. The use of d(10)-phenanthrene as internal standard not only improved the repeatability of the method but allowed quantification of the samples against external aqueous standards. Detection limits ranged between 11 and 26 ng L(-1). PMID:25001331

Cacho, J I; Campillo, N; Viñas, P; Hernández-Córdoba, M

2014-08-22

188

Analysis by gas chromatography-mass spectrometry of the essential oil from the aerial parts of Pimpinella junoniae Ceb. & Ort., gathered in La Gomera, Canary Islands, Spain.  

PubMed

The essential oil from the aerial parts of Pimpinella junoniae Ceb. & Ort., growing in La Gomera, Canary Islands, Spain, was studied by gas chromatography and gas chromatography-mass spectrometry, and 43 constituents were identified. The major components were found to be alpha-zingiberene (20.6%), alpha-pinene (17.9%), (E)-beta-farnesene (9.3%), ar-curcumene (7.4%), beta-phellandrene (7.0%), beta-bisabolene (6.1%) and epoxypseudoisoeugenyl 2-methylbutyrate (6.0%). The decomposition product of epoxypseudoisoeugenol derivatives, 5-methoxy-2-methylbenzofuran (5.7%), moderate amounts of other arylpropanoids with the pseudoisoeugenol skeleton (total percentage, 5.2%) and other compounds such as beta-sesquiphellandrene (3.0%), cis-beta-guaiene (1.5%), alpha-phellandrene (1.5%) and alpha-bisabolol (1.3%), were also found. PMID:14518782

Velasco-Negueruela, A; Pérez-Alonso, M J; Pérez de Paz, P L; Paúl-Palá, J; Sanz, J

2003-09-01

189

The use of multivariate curve resolution methods to improve the analysis of muramic acid as bacterial marker using gas chromatography-mass spectrometry: an alternative method to gas chromatography-tandem mass spectrometry.  

PubMed

In analysis of muramic acid (MA) as bacterial marker, two dominant disturbing factors lead the researchers to use gas chromatography-tandem mass spectrometry (GC-MS/MS) technique instead of gas chromatography-mass spectrometry (GC-MS). These factors are the trace concentration of MA and fundamental disturbance of base line mass channels in GC-MS technique. This study aimed to utilize multivariate curve resolution (MCR) methods combined with GC-MS to improve the analysis of MA. First, the background and noise in GC-MS analysis were corrected and reduced using MCR methods. In addition, the MA overlapped peaks were resolved to its pure chromatographic and mass spectral profiles. Then the two-way response of each component was reconstructed by the outer product of the pure chromatographic and mass spectral profiles. The overall volume integration (OVI) method was used for quantitative determination. The MA peak area was decreased dramatically after the background correction and noise reduction. The findings severely ratify the appropriateness of using MCR techniques combined with GC-MS analysis as a simple, fast and inexpensive method for the analysis of MA in complex mixtures. The proposed method may be considered as an alternative method to GC-MS/MS for thorough analysis of the bacterial marker. PMID:24441017

Moazeni-Pourasil, Roudabeh Sadat; Piri, Farhad; Ghassempour, Alireza; Jalali-Heravi, Mehdi

2014-02-15

190

Characterization and quantitative amino acids analysis of analgesic peptides in cinobufacini injection by size exclusion chromatography, matrix-assisted laser desorption/ionization time of flight mass spectrometry and gas chromatography mass spectrometry.  

PubMed

Cinobufacini injection that comes from the water extract of Bufo bufo gargarizans Cantor skin is widely used for cancer treatment in China. Peptide is one of its major types of constituents, however the biological effects and content of this injection are little reported. In present study, the analgesic effect of peptides was determined and evaluated by in-vivo models. To characterize and quantitatively analyze these peptides, a reliable and efficient method combining size exclusion chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry with amino acid analysis was developed. The peptides presented as a series of analogs with similar molecular weights mostly ranging from 2 to 8 kDa. The amino acid analysis by gas chromatography mass spectrometry (GC-MS) was developed to determine both free and combined amino acids (FAA and CAA) in cinobufacini injection. This method achieved good linearity (R(2) , 0.9909-0.9999) and low limit of detection and quantification. FAA and CAA samples were efficiently analyzed by modified Phenomenex EZ: faast procedure. For the sample analysis, the method showed good repeatability (relative standard deviation, RSD???10%). For most FAA and CAA the mean recoveries were >80% with RSD <10%. The GC-MS based method is useful for quality assurance of both FAA and CAA in cinobufacini injection. PMID:24924921

Wu, Xu; Si, Nan; Bo, Gao; Hu, Hao; Yang, Jian; Bian, Baolin; Zhao, Hai Yu; Wang, Hongjie

2015-01-01

191

CHARACTERIZATION OF ORGANICS IN TANNERY EFFLUENTS BY LIQUID CHROMATOGRAPHY MASS SPECTROMETRY  

EPA Science Inventory

Combined high performance liquid chromatography mass spectrometry using a moving belt interface has been used to study extracts from five tannery and leather finishing industry discharges. Liquid chromatographic separation was performed with a Zorbax CN column using a normal phas...

192

Identification of polychlorinated styrene compounds in heron tissues by gas-liquid chromatography-mass spectrometry.  

PubMed

Unknown compounds detected in Ardea herodias tissues are identified by gas-liquid chromatography-mass spectrometry as residues of octachlorostyrene. Heptachlorostyrene and hexachlorostyrene were tentatively identified. PMID:833106

Reichel, W L; Prouty, R M; Gay, M L

1977-01-01

193

Measuring Deuterium Enrichment of Glucose Hydrogen Atoms by Gas Chromatography/Mass Spectrometry  

E-print Network

We developed a simple and accurate method for determining deuterium enrichment of glucose hydrogen atoms by electron impact gas chromatography mass spectrometry (GC/MS). First, we prepared 18 derivatives of glucose and ...

Antoniewicz, Maciek R.

194

Quantitation of Phenol Levels in Oil of Wintergreen Using Gas Chromatography-Mass Spectrometry with Selected Ion Monitoring  

ERIC Educational Resources Information Center

Industrial application of gas chromatography-mass spectrometry (GC-MS) analysis is a powerful technique that could be used to elucidate components of a complex mixture while offering the benefits of high-precision quantitative analysis. The natural wintergreen oil is examined for its phenol concentration to determine the level of refining…

Sobel, Robert M.; Ballantine, David S.; Ryzhov, Victor

2005-01-01

195

Analysis of polycyclic aromatic hydrocarbons in aqueous samples by large volume injection gas chromatography-mass spectrometry using the through oven transfer adsorption desorption interface.  

PubMed

A new procedure for the determination of 17 polycyclic aromatic hydrocarbons (PAHs) in aqueous samples by large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS) using the Through Oven Transfer Adsorption Desorption (TOTAD) interface with nitrogen for solvent elimination is developed and validated. Up to 75mL of aqueous samples were injected to be sure that good solvent elimination were achieved, although 500µL were sufficient to achieve the required sensitivity.The performance of the developed method can be considered good: the relative standard deviation (RSD), (n=3) was lower than 13.8% for all the target analytes, the concentration of each PAH being 0.25?gL(-1), the limit of detection and limit of quantitation ranged from 21.5 to 211.0?ng?L(-1) and from 71.7 to 703.3ngL(-1) respectively, and the correlation coefficients (R(2)) were all higher than 0.9764 in the 1-16?gL(-1) range. PMID:25882400

Aragón, Álvaro; Toledano, Rosa M; Vázquez, Ana; Villén, Jesús; Cortés, José M

2015-07-01

196

Stir bar sorptive extraction and trace analysis of selected endocrine disruptors in water, biosolids and sludge samples by thermal desorption with gas chromatography-mass spectrometry.  

PubMed

Stir bar sorptive extraction (SBSE) in combination with thermal desorption coupled to gas chromatography-mass spectrometry (GC-MS) was successfully applied to analyze a range of endocrine disrupting compounds (EDCs) in wastewater, solids and sludge. The targeted EDCs include sex steroid hormones, phthalates, alkylphenols and tamoxifen. Recovery for the EDCs using this analytical technique ranged from 44% to 128%. Limit of detection (LOD) of the compounds was 2.0 ng/L for water samples and 0.02 ng/g for solid samples, whereas the limit of quantitation (LOQ) was 5.0 ng/L for water samples and 0.06 ng/g for solid samples. When this analytical technique was applied to measure EDC concentration in a biological nutrient removal (BNR) wastewater treatment plant located in South East Queensland, Australia, the results showed that there were high amounts of phthalates, alkylphenols and female hormones present in the raw influent wastewater and solids. These concentrations were dramatically reduced after passing through the various treatment zones of the bioreactor (anaerobic, aerobic and anoxic). PMID:17706739

Tan, Benjamin L L; Hawker, Darryl W; Müller, Jochen F; Tremblay, Louis A; Chapman, Heather F

2008-01-01

197

Metabonomic analysis of quercetin against the toxicity of chronic exposure to low-level dichlorvos in rats via ultra-performance liquid chromatography-mass spectrometry.  

PubMed

This study aims to determine whether quercetin elicits a protective effect against the toxicity of chronic exposure to low-level DDVP using metabonomic technology. Rats were randomly assigned into the control, DDVP-treated, quercetin-treated, and quercetin plus DDVP-treated groups. DDVP and quercetin were given to rats daily via drinking water and gavage respectively for 90 days. Eighteen metabolites, including the biomarkers of DDVP exposure (dimethyl phosphate, DMP) and quercetin exposure (quercetin and isorhamnetina), were identified from the metabonomic profiles of rat urine using ultra-performance liquid chromatography-mass spectrometry. Compared with the control group, the DDVP-treated group showed statistically significantly increased intensities of indoxyl sulfate, estrone sulfate, cholic acid, deoxycholic acid, p-cresol, p-cresol sulfate, and orotic acid but decreased intensities of suberic acid, citric acid, sebacic acid, hippuric acid, taurine, phosphocreatine, 3-hydroxyanthranilic acid, and kynurenic acid. The tendency of the aforesaid metabolites to change was significantly ameliorated in the quercetin (50mg/kg·bw) plus DDVP (7.2mg/kg·bw)-treated group compared with the DDVP-treated group. However, the levels of these metabolites in the quercetin plus DDVP-treated groups were still significantly different from those of the control group. These results indicate that quercetin has a partial protective effect on DDVP-induced toxicity. PMID:24374570

Wang, Hong; Li, Sifan; Qi, Lei; Xu, Wei; Zeng, Yan; Hou, Yurong; Zhao, Xiujuan; Sun, Changhao

2014-03-01

198

Comparison of photoacoustic radiometry to gas chromatography/mass spectrometry methods for monitoring chlorinated hydrocarbons  

SciTech Connect

A comparison of two methods of gas chromatography mass spectrometry (GCMS) and a nondispersive infrared technique, photoacoustic radiometry (PAR), is presented in the context of field monitoring a disposal site. First is presented an historical account describing the site and early monitoring to provide an overview. The intent and nature of the monitoring program changed when it was proposed to expand the Radiological Waste Site close to the Hazardous Waste Site. Both the sampling methods and analysis techniques were refined in the course of this exercise.

Sollid, J.E.; Trujillo, V.L.; Limback, S.P.; Woloshun, K.A.

1996-03-01

199

An Advanced Analytical Chemistry Experiment Using Gas Chromatography-Mass Spectrometry, MATLAB, and Chemometrics to Predict Biodiesel Blend Percent Composition  

ERIC Educational Resources Information Center

We present a laboratory experiment for an advanced analytical chemistry course where we first focus on the chemometric technique partial least-squares (PLS) analysis applied to one-dimensional (1D) total-ion-current gas chromatography-mass spectrometry (GC-TIC) separations of biodiesel blends. Then, we focus on n-way PLS (n-PLS) applied to…

Pierce, Karisa M.; Schale, Stephen P.; Le, Trang M.; Larson, Joel C.

2011-01-01

200

Quantitative Thin-Layer Chromatography/Mass Spectrometry Analysis of Caffeine Using a Surface Sampling Probe Electrospray Ionization Tandem Mass Spectrometry System  

SciTech Connect

Quantitative determination of caffeine on reversed-phase C8 thin-layer chromatography plates using a surface sampling electrospray ionization system with tandem mass spectrometry detection is reported. The thin-layer chromatography/electrospray tandem mass spectrometry method employed a deuterium-labeled caffeine internal standard and selected reaction monitoring detection. Up to nine parallel caffeine bands on a single plate were sampled in a single surface scanning experiment requiring 35 min at a surface scan rate of 44 {mu}m/s. A reversed-phase HPLC/UV caffeine assay was developed in parallel to assess the mass spectrometry method performance. Limits of detection for the HPLC/UV and thin-layer chromatography/electrospray tandem mass spectrometry methods determined from the calibration curve statistics were 0.20 ng injected (0.50 {mu}L) and 1.0 ng spotted on the plate, respectively. Spike recoveries with standards and real samples ranged between 97 and 106% for both methods. The caffeine content of three diet soft drinks (Diet Coke, Diet Cherry Coke, Diet Pepsi) and three diet sport drinks (Diet Turbo Tea, Speed Stack Grape, Speed Stack Fruit Punch) was measured. The HPLC/UV and mass spectrometry determinations were in general agreement, and these values were consistent with the quoted values for two of the three diet colas. In the case of Diet Cherry Coke and the diet sports drinks, the determined caffeine amounts using both methods were consistently higher (by 8% or more) than the literature values.

Ford, Michael J [ORNL; Deibel, Michael A. [Earlham College; Tomkins, Bruce A [ORNL; Van Berkel, Gary J [ORNL

2005-01-01

201

Quantitative thin-layer chromatography/mass spectrometry analysis of caffeine using a surface sampling probe electrospray ionization tandem mass spectrometry system.  

PubMed

Quantitative determination of caffeine on reversed-phase C8 thin-layer chromatography plates using a surface sampling electrospray ionization system with tandem mass spectrometry detection is reported. The thin-layer chromatography/electrospray tandem mass spectrometry method employed a deuterium-labeled caffeine internal standard and selected reaction monitoring detection. Up to nine parallel caffeine bands on a single plate were sampled in a single surface scanning experiment requiring 35 min at a surface scan rate of 44 mum/s. A reversed-phase HPLC/UV caffeine assay was developed in parallel to assess the mass spectrometry method performance. Limits of detection for the HPLC/UV and thin-layer chromatography/electrospray tandem mass spectrometry methods determined from the calibration curve statistics were 0.20 ng injected (0.50 muL) and 1.0 ng spotted on the plate, respectively. Spike recoveries with standards and real samples ranged between 97 and 106% for both methods. The caffeine content of three diet soft drinks (Diet Coke, Diet Cherry Coke, Diet Pepsi) and three diet sport drinks (Diet Turbo Tea, Speed Stack Grape, Speed Stack Fruit Punch) was measured. The HPLC/UV and mass spectrometry determinations were in general agreement, and these values were consistent with the quoted values for two of the three diet colas. In the case of Diet Cherry Coke and the diet sports drinks, the determined caffeine amounts using both methods were consistently higher (by approximately 8% or more) than the literature values. PMID:16013850

Ford, Michael J; Deibel, Michael A; Tomkins, Bruce A; Van Berkel, Gary J

2005-07-15

202

Methods of analysis by the U. S. Geological Survey National Water Quality Laboratory - determination of organonitrogen herbicides in water by solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selected-ion monitoring  

USGS Publications Warehouse

A method for the isolation of organonitrogen herbicides from natural water samples using solid-phase extraction and analysis 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 cartridges containing octadecyl-bonded porous silica to remove the herbicides. The cartridges are dried using carbon dioxide, and adsorbed herbicides are removed from the cartridges by elution with 1.8 milliliters of hexaneisopropanol (3:1). Extracts of the eluants are analyzed by capillary-column gas chromatography/mass spectrometry with selected-ion monitoring of at least three characteristic ions. The method detection limits are dependent on sample matrix and each particular herbicide. The method detection limits, based on a 100-milliliter sample size, range from 0.02 to 0.25 microgram per liter. Recoveries averaged 80 to 115 percent for the 23 herbicides and 2 metabolites in 1 reagent-water and 2 natural-water samples fortified at levels of 0.2 and 2.0 micrograms per liter.

Sandstrom, Mark W.; Wydoski, Duane S.; Schroeder, Michael P.; Zamboni, Jana L.; Foreman, William T.

1992-01-01

203

Multiresidue analysis of acidic and polar organic contaminants in water samples by stir-bar sorptive extraction-liquid desorption-gas chromatography-mass spectrometry.  

PubMed

The feasibility of stir-bar sorptive extraction (SBSE) followed by liquid desorption in combination with large volume injection (LVI)-in port silylation and gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of a broad range of 46 acidic and polar organic pollutants in water samples has been evaluated. The target analytes included phenols (nitrophenols, chlorophenols, bromophenols and alkylphenols), acidic herbicides (phenoxy acids and dicamba) and several pharmaceuticals. Experimental variables affecting derivatisation yield and peak shape as a function of different experimental PTV parameters [initial injection time, pressure and temperature and the ratio solvent volume/N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) volume] were first optimised by an experimental design approach. Subsequently, SBSE conditions, such as pH, ionic strength, agitation speed and extraction time were investigated. After optimisation, the method failed only for the extraction of most polar phenols and some pharmaceuticals, being suitable for the determination of 37 (out of 46) pollutants, with detection limits for these analytes ranging between 1 and 800 ng/L and being lower than 25 ng/L in most cases. Finally, the developed method was validated and applied to the determination of target analytes in various aqueous environmental matrices, including ground, river and wastewater. Acceptable accuracy (70-130%) and precision values (<20%) were obtained for most analytes independently of the matrix, with the exception of some alkylphenols, where an isotopically labelled internal standard would be required in order to correct for matrix effects. Among the drawbacks of the method, carryover was identified as the main problem even though the Twisters were cleaned repeatedly. PMID:17727869

Quintana, José Benito; Rodil, Rosario; Muniategui-Lorenzo, Soledad; López-Mahía, Purificación; Prada-Rodríguez, Darío

2007-12-01

204

Development of stir-bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry for the analysis of musks in vegetables and amended soils.  

PubMed

The aim of this study was to develop a sensitive and environment-friendly method based on stir-bar sorptive extraction (SBSE) followed by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) to determine 8 synthetic musks (musk ambrette, musk ketone, celestolide, tonalide, galaxolide, phantolide, traseolide, and cashmeran) in vegetables (lettuce, carrot, and pepper) and amended soil samples. In a first step sorptive extraction was studied both in the headspace (HSSE) and in the immerse mode (SBSE). The best results were obtained in the immersion mode which was further studied. The influence of the main factors: methanol (20%) and NaCl addition (0%), extraction temperature (40°C) and time (180 min), extraction solvent volume (9 mL) and stirring rate (600 rpm) on the efficiency of SBSE was evaluated by means of experimental designs. In the case of TD, desorption time (10 min), desorption temperature (300°C), cryo-focusing temperature (-30°C), vent flow (75 mL/min) and vent pressure (7.2 psi) were studied using both a fractioned factorial design and a central composite design (CCD). The method was validated in terms of apparent recoveries (AR%), method detection limits (MDLs) and precision at two different concentration levels. Although quantification using instrumental calibration rendered odd results in most of the cases, satisfactory recoveries (74-126%) were obtained in the case of matrix-matched calibration approach for all of the analytes and matrices studied at the two concentration levels evaluated. MDLs in the range of 0.01-0.8 ng/g and 0.01-1.1 ng/g were obtained for vegetables and amended soil samples, respectively. RSD values within 1-23% were obtained for all the analytes and matrices. Finally, the method was applied to the determination of musks in vegetable and amended soil samples. PMID:24491767

Aguirre, Josu; Bizkarguenaga, Ekhiñe; Iparraguirre, Arantza; Fernández, Luis Ángel; Zuloaga, Olatz; Prieto, Ailette

2014-02-17

205

MICELLAR ELECTROKINETIC CHROMATOGRAPHY-MASS SPECTROMETRY (R823292)  

EPA Science Inventory

The combination of micellar electrokinetic chromatography (MEKC) with mass spectrometry (MS) is very attractive for the direct identification of analyte molecules, for the possibility of selectivity enhancement, and for the structure confirmation and analysis in a MS-MS mode. The...

206

Quantitative analysis of polar lipids in the nanoliter level of rat serum by liquid chromatography/mass spectrometry/mass spectrometry  

Technology Transfer Automated Retrieval System (TEKTRAN)

Polar lipids in serum, including lysophospholipids (LPLs) and free fatty acids (FFAs), have a broad range of biological activities and require a suitable method for their quantitative analysis. Conventional methods use multistep procedures to simultaneously purify and analyze polar lipids and non-po...

207

Chlorinated hydrocarbons in the atmosphere - Analysis at the parts-per-trillion level by GC-MS. [Gas Chromatography-Mass Spectrometry  

NASA Technical Reports Server (NTRS)

The propellant gases (Freons) used in aerosol spray cans can diffuse into the earth's upper atmosphere where they can react with the unfiltered ultraviolet radiation from the sun to reduce the earth's protective ozone layer. These Freons have been identified commonly by gas chromatography. Mass spectrometer data confirm other reports on the widespread concentrations of the Freons in the troposphere and demonstrate the presence of Freon 113 which has not been previously identified.

Tyson, B. J.

1975-01-01

208

Automated determination of carboxyhemoglobin contents in autopsy materials using head-space gas chromatography\\/mass spectrometry  

Microsoft Academic Search

To establish a method for the routine analysis of carboxyhemoglobin (COHb) in autopsy materials including those which have undergone postmortem changes, e.g. thermo-coagulation, putrifaction and contamination, an automated head-space gas chromatography\\/mass spectrometry (GC\\/MS) analysis was utilized. The procedure consisted of preparation of the sample in a vial and a carbon monoxide (CO) saturated sample, for estimation of hemoglobin content, in

Shigeki Oritani; Bao-Li Zhu; Kaori Ishida; Keiko Shimotouge; Li Quan; Masaki Q Fujita; Hitoshi Maeda

2000-01-01

209

Derivatization of pinacolyl alcohol with phenyldimethylchlorosilane for enhanced detection by gas chromatography-mass spectrometry.  

PubMed

A derivatization procedure for the qualitative gas chromatography-mass spectrometry (GC-MS) analysis of pinacolyl alcohol (PA) that employs phenyldimethylchlorosilane (PhDMClS) and the promoter N-methylimidazole is described. While PA, underivatized, can be detected using conventional gas chromatographic methods, its polarity and low boiling point make its detection in complex matrices challenging. The silylation procedure described herein generates a PA-derivative exhibiting an increased on-column retention time, thus shifting its GC-MS signal away from commonly encountered, volatile, interfering analytes. Derivatized PA could be distinguished from other PhDMClS-derivatized isomeric alcohols by its unique retention time and mass spectrum. The derivatization was demonstrated to perform well in the GC-MS analysis and identification of PA in samples from Proficiency Tests administered by the Organisation for the Prohibition of Chemical Weapons (OPCW). PMID:24481624

Albo, Rebecca L F; Valdez, Carlos A; Leif, Roald N; Mulcahy, Heather A; Koester, Carolyn

2014-08-01

210

Enhancement of the capabilities of liquid chromatography-mass spectrometry with derivatization: general principles and applications.  

PubMed

The integration of liquid chromatography-mass spectrometry (LC-MS) with derivatization is a relatively new and unique strategy that could add value and could enhance the capabilities of LC-MS-based technologies. The derivatization process could be carried out in various analytical steps, for example, sampling, storage, sample preparation, HPLC separation, and MS detection. This review presents an overview of derivatization-based LC-MS strategy over the past 10 years and covers both the general principles and applications in the fields of pharmaceutical and biomedical analysis, biomarker and metabolomic research, environmental analysis, and food-safety evaluation. The underlying mechanisms and theories for derivative reagent selection are summarized and highlighted to guide future studies. PMID:21557289

Xu, Fengguo; Zou, Li; Liu, Ying; Zhang, Zunjian; Ong, Choon Nam

2011-01-01

211

Group separation and gas chromatography--mass spectrometry of conjugated steroids in plasma.  

PubMed

A method is described for analysis of metabolic profiles of conjugated steroids in plasma. Steroids are extracted by Amberlite XAD-2 or Sep-Pak C18 cartridges at 60 64 C in the presence of triethylamine sulphate and separated into unconjugated neutral and phenolic compounds, glucuronide, monosulphate and disulphate conjugate groups by chromatography on the lipophilic strong anion exchanger triethylaminohydroxypropyl Sephadex LH-20 (TEAP-LH-20). The conjugate moiety is hydrolyzed by brief enzymatic or solvolytic procedures and released steroids are separated into a neutral and a phenolic fraction on TEAP-LH-20. The O-methyloxime and trimethylsilyl ether derivatives of the steroids are analyzed by glass capillary column gas liquid chromatography and gas chromatography mass spectrometry. Examples of the application of the method to analysis of conjugated steroids in plasma from pregnant women are given. PMID:6827836

Axelson, M; Sahlberg, B L

1983-03-01

212

[Effect of menthol cigarette on rats for metabonomics by liquid chromatography-mass spectrometry].  

PubMed

A liquid chromatography-mass spectrometry (LC-MS) method was developed for the metabonomics study of menthol cigarette effect on rats. Urines from three groups of rats were analyzed, including control rats, rats treated with menthol cigarette and rats treated with normal cigarette, and the data were processed by the method of principal component analysis (PCA). The PCA score plot showed that the metabolic difference between the rats treated with menthol cigarette and the control rats was smaller than that between the rats treated with normal cigarette and the control rats. Based on the PCA score plot, eight important metabolites, for example, kynurenic acid, were found and identified. Their relative concentration changes among the three groups further indicated that menthol cigarette maybe decrease the metabolic effect on rats. PMID:21261044

Shi, Xianzhe; He, Zhihui; Dou, Abo; Zhang, Fengxia; Lian, Wenliu; Xu, Guowang

2010-08-01

213

Screening for Annonaceous acetogenins in bioactive plant extracts by liquid chromatography/mass spectrometry.  

PubMed

The Annonaceous acetogenins are amenable to analysis by liquid chromatography/mass spectrometry (LC/MS) using the electrospray positive-ion mode. Under conditions of atmospheric pressure in-source collision-induced dissociation (APICID), the acetogenins reproducibly provided characteristic ion patterns and fragment ions. Accordingly, the presence of these biologically interesting acetogenins and other derivatives in plant extracts and chromatographic fractions can be readily detected by analyzing selected ion chromatograms. LC/MS screening of a bioactive crude methanol-soluble fraction of Rollinia mucosa detected the presence of some 40 known acetogenins in this plant extract, in addition to four new acetogenins of diverse structure. This rapid and relatively uncomplicated selected ionization procedure should also prove suitable for the screening of many other structural families of natural products. PMID:9090866

Gu, Z M; Zhou, D; Wu, J; Shi, G; Zeng, L; McLaughlin, J L

1997-03-01

214

Heparin stability by determining unsubstituted amino groups using hydrophilic interaction chromatography mass spectrometry.  

PubMed

The thermal instability of the anticoagulant heparin is associated, in part, with the solvolytic loss of N-sulfo groups. This study describes a new method to assess the increased content of unsubstituted amino groups present in thermally stressed and autoclave-sterilized heparin formulations. N-Acetylation of heparin samples with acetic anhydride-d6 is followed by exhaustive heparinase treatment and disaccharide analysis by hydrophilic interaction chromatography mass spectrometry (HILIC-MS). The introduction of a stable isotopic label provides a sensitive probe for the detection and localization of the lost N-sulfo groups, potentially providing valuable insights into the degradation mechanism and the reasons for anticoagulant potency loss. PMID:24909446

Fu, Li; Li, Lingyun; Cai, Chao; Li, Guoyun; Zhang, Fuming; Linhardt, Robert J

2014-09-15

215

Determination of tetrahydrozoline in urine and blood using gas chromatography-mass spectrometry (GC-MS).  

PubMed

Tetrahydrozoline, a derivative of imidazoline, is widely used for the symptomatic relief of conjunctival and nasal congestion; however, intentional or unintentional high doses can result in toxicity manifested by hypotension, tachycardia, and CNS depression. The detection of the drug in blood and urine is helpful in the diagnosis and management of a toxic patient. For the analysis, plasma, serum, or urine is added to a tube containing alkaline buffer and organic extraction solvents, and tetrahydrozoline from the sample is extracted into the organic phase by gentle mixing. After centrifugation, the upper organic solvent layer containing the drug is removed and dried under stream of nitrogen at 40 degrees C. The residue is reconstituted in a hexane-ethanol mixture and analyzed using gas-chromatography-mass spectrometry. Quantitation of the drug is done by comparing responses of unknown sample to the responses of the calibrators using selected ion monitoring. Naphazoline is used as an internal standard. PMID:20077102

Peat, Judy; Garg, Uttam

2010-01-01

216

Gas Chromatography-Mass Spectrometry-Based Metabolic Profiling of Cerebrospinal Fluid from Epileptic Dogs  

PubMed Central

ABSTRACT Epilepsy is a common neurological disorder with seizures, but diagnostic approaches in veterinary clinics remain limited. Cerebrospinal fluid (CSF) is a body fluid used for diagnosis in veterinary medicine. In this study, we explored canine epilepsy diagnostic biomarkers using gas chromatography-mass spectrometry (GC-MS)-based metabolic profiling of CSF and multivariate data analysis. Profiles for subjects with idiopathic epilepsy differed significantly from those of healthy controls and subjects with symptomatic epilepsy. Among 60 identified metabolites, the levels of 20 differed significantly among the three groups. Glutamic acid was significantly increased in idiopathic epilepsy, and some metabolites including ascorbic acid were changed in both forms of epilepsy. These findings show that metabolic profiles of CSF differ between idiopathic and symptomatic epilepsy and that metabolites including glutamic acid and ascorbic acid in CSF may be useful for diagnosis of canine epilepsy. PMID:24334864

HASEGAWA, Tetsuya; SUMITA, Maho; HORITANI, Yusuke; TAMAI, Reo; TANAKA, Katsuhiro; KOMORI, Masayuki; TAKENAKA, Shigeo

2013-01-01

217

Isolation, enrichment, and analysis of erythropoietins in anti-doping analysis by receptor-coated magnetic beads and liquid chromatography-mass spectrometry.  

PubMed

Human erythropoietin (hEPO) is an erythropoiesis stimulating hormone frequently employed in antianemia therapy. Its capability to increase the amount of red blood cells however makes hEPO and its derivatives also attractive to dishonest athletes aiming at an artificial and illicit enhancement of their endurance performance. A major objective of the international antidoping fight is the elimination of drug misuse and prevention of severe adverse effects caused by nontherapeutic administrations of highly potent drugs. The emergence of novel and innovative erythropoietin-mimetic agents (EMAs) has been continuously growing in the last years, and the option of using dedicated monoclonal antibodies (mAb) for analytical and sample preparation approaches is gradually reaching limits. In the present study the common ability and property of all EMAs, to bind on the human erythropoietin receptor (hEPOR), is therefore exploited. An alternative methodology to isolate and analyze EMAs, in particular endogenous EPO and the recombinant forms EPOzeta, darbepoetin alfa, and C.E.R.A., from human urine is described, employing conventional ultrafiltration for preconcentration of the target analytes followed by EMA-specific isolation via hEPOR-bound magnetic beads. Analytical data were generated by means of gel-based electrophoretic analysis and nanoliquid chromatography/high resolution/high accuracy tandem mass spectrometry. Limits of detection enabled by the established sample preparation protocols were approximately 20 pg/mL for EPOzeta, 30 pg/mL for darbepoetin alfa, and 80 pg/mL for C.E.R.A. PMID:25423444

Vogel, Matthias; Blobel, Mike; Thomas, Andreas; Walpurgis, Katja; Schänzer, Wilhelm; Reichel, Christian; Thevis, Mario

2014-12-16

218

PERFORMANCE EVALUATION OF PARTICLE BEAM LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY FOR THE MEASUREMENT OF ACID HERBICIDES  

EPA Science Inventory

Particle beam liquid chromatography/mass spectrometry (LC/MS) was evaluated for the measurement of acid herbicides. n acetic acid/ammonium acetate/methano1 solvent system with a C-8 reversed Phase column gave baseline resolution of all target analytes. etection limits in the full...

219

APPLICATION OF A SPRAY DEPOSITION METHOD FOR REVERSED PHASE LIQUID CHROMATOGRAPHY-MASS SPECTROMETRY  

EPA Science Inventory

Four coal gasification wastewater samples were analyzed for nonvolatile and polar organics by liquid chromatography-mass spectrometry (LC/MS). Samples were separated on a reverse phase liquid chromatographic column using an aqueous solvent as the eluant. A special spray depositio...

220

Thermal degradation of deoxybenzoin polymers studied by pyrolysis-gas chromatography/mass spectrometry  

E-print Network

Thermal degradation of deoxybenzoin polymers studied by pyrolysis-gas chromatography by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The polymers were synthesized Available online 29 March 2008 Keywords: Flame-retardant polymers Thermal degradation Pyrolysis-gas

221

Incorporation of Gas Chromatography-Mass Spectrometry into the Undergraduate Organic Chemistry Laboratory Curriculum  

ERIC Educational Resources Information Center

Gas chromatography-mass spectrometry (GC-MS) is a powerful analytical tool for detection, identification, and quantification of many volatile organic compounds. However, many colleges and universities have not fully incorporated this technique into undergraduate teaching laboratories despite its wide application and ease of use in organic…

Giarikos, Dimitrios G.; Patel, Sagir; Lister, Andrew; Razeghifard, Reza

2013-01-01

222

Determination of Cyanide in Blood by Isotope Dilution Gas Chromatography-Mass Spectrometry  

Microsoft Academic Search

Background: Cyanide (CN) is a lethal toxin. Quantifi- cation in blood is necessary to indicate exposure from many sources, including food, combustion byproducts, and terrorist activity. We describe an automated proce- dure based on isotope-dilution gas chromatography- mass spectrometry (ID GC\\/MS) for the accurate and rapid determination of CN in whole blood. Methods: A known amount of isotopically labeled po-

Karen E. Murphy; Michele M. Schantz; Therese A. Butler; Bruce A. Benner; Laura J. Wood; Gregory C. Turk

223

DEVELOPMENTS IN DIRECT THERMAL EXTRACTION GAS CHROMATOGRAPHY-MASS SPECTROMETRY OF FINE AEROSOLS  

EPA Science Inventory

This examines thermal extraction gas chromatography-mass spectrometry (TE/GC/MS) applied to aerosols collected on filters. Several different TE/GC/MS systems as a group have speciated hundreds of individual organic constituents in ambient fine aerosols. Molecular marker source ap...

224

Metabolomic identification of potential phospholipid biomarkers for chronic glomerulonephritis by using high performance liquid chromatography–mass spectrometry  

Microsoft Academic Search

Plasma phospholipids metabolic profile of chronic glomerulonephritis was investigated using high performance liquid chromatography\\/mass spectrometry (LC\\/MS) and principal component analysis. The plasma samples of 18 patients with chronic glomerulonephritis, 17 patients with chronic renal failure (CRF) without renal replacement therapy and 18 healthy persons were collected and analyzed. It was found that combination of the LC\\/MS technique with PCA can

Lewen Jia; Chang Wang; Sumin Zhao; Xin Lu; Guowang Xu

2007-01-01

225

Detection and identification of carprofen and its in vivo metabolites in greyhound urine by capillary gas chromatography–mass spectrometry  

Microsoft Academic Search

Rimadyl® (carprofen) was administered orally to the racing greyhound at a dose of 2.2 mg kg?1. Following both alkaline and enzymatic hydrolysis, postadministration urine samples were extracted by mixed mode solid-phase extraction (SPE) cartridges to identify target analyte(s) for forensic screening and confirmatory analysis methods. The acidic isolates were derivatised as trimethylsilyl ethers (TMS) and analysed by gas chromatography–mass spectrometry

M. C. Dumasia; A. Ginn; W. Hyde; J. Peterson; E. Houghton

2003-01-01

226

Differentiating organically and conventionally grown oregano using ultraperformance liquid chromatography mass spectrometry (UPLC-MS), headspace gas chromatography with flame ionization detection (headspace-GC-FID), and flow injection mass spectrum (FIMS) fingerprints combined with multivariate data analysis.  

PubMed

Ultraperformance liquid chromatography mass spectrometry (UPLC-MS), flow injection mass spectrometry (FIMS), and headspace gas chromatography (headspace-GC) combined with multivariate data analysis techniques were examined and compared in differentiating organically grown oregano from that grown conventionally. It is the first time that headspace-GC fingerprinting technology is reported in differentiating organically and conventionally grown spice samples. The results also indicated that UPLC-MS, FIMS, and headspace-GC-FID fingerprints with OPLS-DA were able to effectively distinguish oreganos under different growing conditions, whereas with PCA, only FIMS fingerprint could differentiate the organically and conventionally grown oregano samples. UPLC fingerprinting provided detailed information about the chemical composition of oregano with a longer analysis time, whereas FIMS finished a sample analysis within 1 min. On the other hand, headspace GC-FID fingerprinting required no sample pretreatment, suggesting its potential as a high-throughput method in distinguishing organically and conventionally grown oregano samples. In addition, chemical components in oregano were identified by their molecular weight using QTOF-MS and headspace-GC-MS. PMID:25050447

Gao, Boyan; Qin, Fang; Ding, Tingting; Chen, Yineng; Lu, Weiying; Yu, Liangli Lucy

2014-08-13

227

Detecting trace components in liquid chromatography/mass spectrometry data sets with two-dimensional wavelets  

NASA Astrophysics Data System (ADS)

TWiGS (two-dimensional wavelet transform with generalized cross validation and soft thresholding) is a novel algorithm for denoising liquid chromatography-mass spectrometry (LC-MS) data for use in "shot-gun" proteomics. Proteomics, the study of all proteins in an organism, is an emerging field that has already proven successful for drug and disease discovery in humans. There are a number of constraints that limit the effectiveness of liquid chromatography-mass spectrometry (LC-MS) for shot-gun proteomics, where the chemical signals are typically weak, and data sets are computationally large. Most algorithms suffer greatly from a researcher driven bias, making the results irreproducible and unusable by other laboratories. We thus introduce a new algorithm, TWiGS, that removes electrical (additive white) and chemical noise from LC-MS data sets. TWiGS is developed to be a true two-dimensional algorithm, which operates in the time-frequency domain, and minimizes the amount of researcher bias. It is based on the traditional discrete wavelet transform (DWT), which allows for fast and reproducible analysis. The separable two-dimensional DWT decomposition is paired with generalized cross validation and soft thresholding. The Haar, Coiflet-6, Daubechie-4 and the number of decomposition levels are determined based on observed experimental results. Using a synthetic LC-MS data model, TWiGS accurately retains key characteristics of the peaks in both the time and m/z domain, and can detect peaks from noise of the same intensity. TWiGS is applied to angiotensin I and II samples run on a LC-ESI-TOF-MS (liquid-chromatography-electrospray-ionization) to demonstrate its utility for the detection of low-lying peaks obscured by noise.

Compton, Duane C.; Snapp, Robert R.

2007-09-01

228

Phosphorothioate oligonucleotide quantification by ?-liquid chromatography-mass spectrometry.  

PubMed

Phosporothioate oligonucleotides represent an important class of therapeutic oligonucleotides, in which none-bridging oxygen atoms of the phosphate groups are replaced by sulfur. These oligonucleotides are designed to treat disease by modulating gene expression of an affected individual. As the development and application of these therapeutical oligonucleotides require analytical support, the development, validation, and application of an assay for the quantitative analysis of a phosporothioate oligonucleotide in rat plasma is described. The method employs ion-pair reversed-phase chromatography on a monolithic capillary column with acetonitrile gradients in cyclohexyldimethylammonium acetate for separation and high-resolution tandem mass spectrometry for detection of nucleic acids. Chromatographic parameters (i.e. column temperature, mobile phase composition) as well as mass spectrometric parameters (i.e. spray voltage, gas flow, and capillary position, scan mode) have been optimized for sensitive oligonucleotide quantification. Furthermore, a solid-phase extraction method was developed which enabled processing of 10 ?l of plasma. The five-point calibration curve showed linearity over the range of concentrations from 100 to 1,000 nM of the oligonucleotide. The limit of detection was 50 nM. The intra- and inter-day precision and accuracies were always better than 10.2 %. Using this assay, we performed a pharmacokinetic study of the phosporothioate oligonucleotide in rat treated with a single intravenous dose of 0.39 ?mol/kg. The assay sensitivity was sufficient to study the early phase elimination of the oligonucleotide. Small amounts of the oligonucleotide were detectable up to 3 h after dosing. PMID:22806756

Erb, Robert; Leithner, Katharina; Bernkop-Schnürch, Andreas; Oberacher, Herbert

2012-12-01

229

High-Performance Liquid Chromatography-Mass Spectrometry.  

ERIC Educational Resources Information Center

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

Vestal, Marvin L.

1984-01-01

230

MATRIX EFFECTS IN LIQUID CHROMATOGRAPHY-MASS SPECTROMETRY  

Microsoft Academic Search

Despite their enormous utility and diffusion, atmospheric pressure ionization mass spectrometry techniques are subjected to relevant drawbacks called matrix effects (ME). These effects could be summarized in matrix-dependent signal suppression or enhancement that could lead to erroneous quantitative results. The most important method parameters as well as linearity, precision, and accuracy could be modified due to interfering compounds present in

Achille Cappiello; Giorgio Famiglini; Pierangela Palma; Helga Trufelli

2010-01-01

231

Capillary liquid chromatography-mass spectrometry for the rapid identification and quantification of almond flavonoids.  

PubMed

A rapid negative ion ESI high-performance capillary liquid chromatography-mass spectrometry method was developed to identify and quantify flavonoids (e.g., flavanols, flavonols, flavanones and glycosides). Fifteen standards and two varieties of almond skin extract powder (Carmel and Nonpareil) were used to demonstrate the chromatographic separation, reproducibility and accuracy of the method that employed a 150 mm x 0.3 mm ChromXP 3C18-EP-120 column. All standards eluted in less than 10 min, providing a 9-12x reduction in analysis time compared to existing methods (90-120 min). However, isomers (e.g., catechin/epicatechin and galactosides/glucosides) were not resolved and, therefore, identified and quantified collectively. RSDs for retention time and peak area reproducibility (mass spectrometry data) were <0.5% and <5.0%, respectively. Peak area reproducibility was greatly improved (from a RSD>10%) after the implementation of a low-flow metal needle in the ESI source. Quantitation by mass spectrometry also afforded a % error less than 5% for most compounds. PMID:18407280

Hughey, Christine A; Wilcox, Bruce; Minardi, Carina S; Takehara, Chiyo W; Sundararaman, Meenakshi; Were, Lilian M

2008-05-30

232

Optimisation of ion trap parameters for the quantification of chlormequat by liquid chromatography/mass spectrometry and the application in the analysis of pear extracts.  

PubMed

Optimisation of the activation parameters for ion trap mass spectrometric analysis of the chlormequat cation using simplex optimisation enabled the product ion (m/z 58) response to be improved 1000-fold. A comparison of the sensitivity of the optimised ion trap mass spectrometer with that of a triple quadrupole mass spectrometer for liquid chromatography/tandem mass spectrometry (LC/MS/MS) showed that similar limits of detection (LODs) could be achieved. For the MS/MS transition of the (35)Cl precursor to the most abundant product, LODs were 0.8 ng cation mL(-1) (0.004 mg cation kg(-1) pear equivalent) and 1.0 ng cation mL(-1) (0.005 mg cation kg(-1) pear equivalent) on the triple quadrupole and ion trap instrument, respectively. PMID:10623939

Evans, C S; Startin, J R; Goodall, D M; Keely, B J

2000-01-01

233

Gas chromatography-mass spectrometry of Alternaria mycotoxins  

Microsoft Academic Search

Heptafluorobutyrate (HFB) derivatives have not previously been used for GC of Alternative mycotoxins. Capillary (0.5 ?m film) GC-mass spectrometry (MS) showed that full and partial derivatives of alternariol (AOH), alternariol monomethyl ether (AME) and altenuene (ALT); a structurally uncharacterized derivative of altertoxin I (ALTX-I); and a tris-HFB derivative of tenuazonic acid (TA) were formed with heptafluorobutyric anhydride and a basic

P. M. Scott; D. Weber; S. R. Kanhere

1997-01-01

234

Analysis of ketamine and norketamine in urine by automatic solid-phase extraction (SPE) and positive ion chemical ionization–gas chromatography–mass spectrometry (PCI–GC–MS)  

Microsoft Academic Search

Ketamine (KT) is widely abused for hallucination and also misused as a “date-rape” drug in recent years. An analytical method using positive ion chemical ionization–gas chromatography–mass spectrometry (PCI–GC–MS) with an automatic solid-phase extraction (SPE) apparatus was studied for the determination of KT and its major metabolite, norketamine (NK), in urine. Six ketamine suspected urine samples were provided by the police.

Eun-mi Kim; Ju-seon Lee; Sang-kil Choi; Mi-ae Lim; Hee-sun Chung

2008-01-01

235

Gas chromatography/mass spectrometry methods applied for the analysis of a Round Robin sample containing materials present in samples of works of art  

NASA Astrophysics Data System (ADS)

The Users' Group for Mass Spectrometry and Chromatography (MaSC) was established as a discussion forum for scientists involved in the study of artworks and cultural artefacts who wish to exchange information regarding sampling strategies and protocols, preparation of samples, chromatographic and mass spectrometric analysis, data treatment and interpretation of results. Comparing protocols and different approaches to the interpretation of results requires the use of standard reference materials and Round Robin tests. To this end, an artificial, complex Round Robin sample was sent to fifteen laboratories specializing in the analysis of cultural materials. Ten of the participants analyzed the sample and reported their results, which were anonymously discussed at the MaSC meeting in Philadelphia, September 2007. In this paper, the results of the confirming GC/MS analysis of the sample by the author are presented and compared with the results of the participants. The confirming analysis was performed with thermally assisted hydrolysis and methylation GC/MS in combination with pyrolysis, and by a combined method for the analysis of proteins and carbohydrates. A number of different instrumental setups and methods were used by the Round Robin participants. The results show that stepwise extraction followed by different types of derivatization is a successful approach for the analysis and identification of complex samples. A disadvantage is the need for relatively large samples, which are not always available in practice. Pyrolysis with or without tetramethylammonium hydroxide (TMAH) or hexamethyldisilazane (HMDS) was used by four of the participants. The results show that thermally assisted hydrolysis and methylation GC/MS in combination with pyrolysis is a powerful technique for the analysis of multi-component samples. The presence of gums and proteins can be indicated. Synthetic resins such as acrylics can also be analyzed in combination with the traditional binders and resins.

van Keulen, Henk

2009-07-01

236

Identification of new flavonols in hybrid grapes by combined liquid chromatography-mass spectrometry approaches.  

PubMed

Grape flavonols are involved in the phenomenon of copigmentation in red wines. These compounds are characterised by nutraceutical properties, have antioxidant activity and are studied for chemotaxonomy of grapes. In general, hybrid grapes are characterised by presence of polyphenols often qualitatively and quantitatively different from Vitis vinifera varieties. In this work, flavonols of 34 hybrid grape varieties (22 red and 12 white) produced by crossing of V. vinifera, Vitis riparia, Vitis labrusca, Vitis lincecumii and Vitis rupestris species, were studied. Compounds were characterised by combining different liquid chromatography/mass spectrometry (LC/MS) methods: precursor-ion and neutral-loss multiple-reaction-monitoring (MRM), and high-resolution mass spectrometry. Twenty-four glycoside flavonols were identified, including 4 quercetin, 5 myricetin, 4 kaempferol, 3 isorhamnetin, 2 laricitrin, 3 syringetin and 3 dihydroflavonol derivatives; myricetin hexoside-glucuronide, myricetin O-di-hexoside, syringetin O-di-hexoside, isorhamnetin rutinoside and kaempferol rutinoside were found in grape for the first time. Statistical analysis (PCA and cluster analysis) divided the samples in four groups on the basis of their flavonol profiles. PMID:24912722

De Rosso, M; Tonidandel, L; Larcher, R; Nicolini, G; Dalla Vedova, A; De Marchi, F; Gardiman, M; Giust, M; Flamini, R

2014-11-15

237

Study of the microbiodegradation of terpenoid resin-based varnishes from easel painting using pyrolysis-gas chromatography-mass spectrometry and gas chromatography-mass spectrometry.  

PubMed

The alterations produced by microbiological attack on terpenoid resin-based varnishes from panel and canvas paintings have been evaluated using pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) and gas chromatography-mass spectrometry (GC-MS). The proposed methods include the on-line derivatisation of drying oils and diterpenoid resins using hexamethyldisilazane during pyrolysis and the application of methyl chloroformate as a derivatisation reagent for triterpenoid resins in GC-MS. Two types of specimens, consisting of model oil medium prepared from linseed oil and model spirit varnishes prepared from colophony and mastic resins dissolved in turpentine, have been used as reference materials. For a series of specimens upon which different genera of bacteria and fungi were inoculated and encouraged to grow, analyses indicated that no mechanisms that commonly occur during the attack of enzymes on drying oils and terpenoid biodegraders were observed to occur in the oil medium and varnishes studied. Thus, the degradation pathways observed in the performed trials usually occur as consequence of natural ageing. Specific trials consisting of the application of biocides to uninoculated colophony varnish resulted in the identification of processes that produce undesirable degradation of the varnish due to interactions between the biocide and the varnish components. Finally, the studied biocides--Biotin, New-Des and Nipagine--generally exhibited good inhibiting effects on the microorganisms studied, although some interesting differences were found between them regarding the application method and type of biocide. PMID:16826370

Doménech-Carbó, María Teresa; Osete-Cortina, Laura; de la Cruz Cañizares, Juana; Bolívar-Galiano, Fernando; Romero-Noguera, Julio; Fernández-Vivas, María Antonia; Martín-Sánchez, Inés

2006-08-01

238

Methods of Analysis by the U.S. Geological Survey Organic Geochemistry Research Group?Determination of acetamide herbicides and their degradation products in water using online solid-phase extraction and liquid chromatography/mass spectrometry  

USGS Publications Warehouse

An analytical method for the determination of 6 acetamide herbicides (acetochlor, alachlor, dimethenamid, flufenacet, metolachlor, and propachlor) and 16 of their degradation products in natural water samples using solid-phase extraction and liquid chromatography/mass spectrometry is described in this report. Special consideration was given during the development of the method to prevent the formation of degradation products during the analysis. Filtered water samples were analyzed using octadecylsilane as the solid-phase extraction media on online automated equipment followed by liquid chromatography/mass spectrometry. The method uses only 10 milliliters of sample per injection. Three different water-sample matrices, a reagent-water, a ground-water, and a surface-water sample spiked at 0.10 and 1.0 microgram per liter, were analyzed to determine method performance. Method detection limits ranged from 0.004 to 0.051 microgram per liter for the parent acetamide herbicides and their degradation products. Mean recoveries for the acetamide compounds in the ground- and surface-water samples ranged from 62.3 to 117.4 percent. The secondary amide of acetochlor/metolachlor ethanesulfonic acid (ESA) was recovered at an average rate of 43.5 percent. The mean recoveries for propachlor and propachlor oxanilic acid (OXA) were next lowest, ranging from 62.3 to 95.5 percent. Mean recoveries from reagent-water samples ranged from 90.3 to 118.3 percent for all compounds. Overall the mean of the mean recoveries of all compounds in the three matrices spiked at 0.10 and 1.0 microgram per liter ranged from 89.9 to 100.7 percent, including the secondary amide of acetochlor/metolachlor ESA and the propachlor compounds. The acetamide herbicides and their degradation products are reported in concentrations ranging from 0.05 to 2.0 micrograms per liter. The upper concentration limit is 2.0 micrograms per liter for all compounds without dilution. With the exception of the secondary amide of acetochlor/metolachlor ESA, good precision and accuracy for the chloroacetanalide herbicides and their degradation compounds were demonstrated for the method in buffered reagent water, ground water, and surface water. The extraction method as used did not optimize the recovery of the secondary amide of acetochlor/metolachlor ESA.

Lee, E.A.; Strahan, A.P.

2003-01-01

239

In Vitro Antibacterial Activity, Gas Chromatography–Mass Spectrometry Analysis of Woodfordia fruticosa Kurz. Leaf Extract and Host Toxicity Testing With In Vitro Cultured Lymphocytes From Human Umbilical Cord Blood  

PubMed Central

Objectives To locate a plant with suitable phytochemicals for use as antimicrobial agents to control multidrug-resistant (MDR) bacteria as a complementary medicine, without host toxicity as monitored through cultured lymphocytes from human umbilical cord blood. Methods The methanol crude leaf extract of the plant Woodfordia fruticosa was subjected to antimicrobial assay in vitro with nine pathogenic MDR bacteria from clinical samples. This was followed by bioassay-guided fractionation with seven non-polar to polar solvents, gas chromatography–mass spectrometry analysis of the n-butanol fraction, and monitoring of the host toxicity of the leaf extract with in vitro grown lymphocytes from human umbilical cord blood. Results The leaf extract of W. fruticosa had a controlling capacity for MDR bacteria. The minimum inhibitory concentration and minimum bactericidal concentration of the n-butanol fraction were < 1.89 mg/mL extract and 9.63 mg/mL extract, respectively. The gas chromatography–mass spectrometry spectrum of the n-butanol fraction confirmed the presence of 13 peaks of different compounds with retention times of 9.11 minutes, 9.72 minutes, 10.13 minutes, 10.78 minutes, 12.37 minutes, 12.93 minutes, 18.16 minutes, 21.74 minutes, 21.84 minutes, 5.96 minutes, 12.93 minutes, 24.70 minutes, and 25.76 minutes. The six leading compounds were: diethyl phthalate: IUPAC name: diethyl benzene-1,2-dicarboxylate; 5-methyl-2-(1-methylethyl) phenol: IUPAC name: 5-methyl-2-propan-2-ylphenol; (E )-3,7-dimethylocta-2,6-diene-1-thiol: IUPAC name: (2Z)-3,7-dimethylocta-2,6-diene-1-thiol; 2,6,10-dodecatrien-1-ol, 3,7,11-trimethyl-, (E,E ): IUPAC name: 2,6,10-dodecatrien-1-ol; 3,7,11-trimethyl-, (E,E); 2-methoxy-4-(2-propenyl) phenol: IUPAC name: 2-methoxy-4-[(1E)-prop-1-en-1-yl]phenol; hexadecanoic acid: IUPAC name: hexadecanoic acid. Conclusion The presence of antimicrobial compounds that are therapeutically potent against MDR bacteria was confirmed in W. fruticosa. The crude leaf extract showed no host toxicity with human lymphocytes; the n-butanol fraction of the extract was the most suitable bioactive fraction. The terpenes isolated were: 5-methyl-2-(1-methylethyl) phenol, 2-methoxy-4-(2-propenyl) phenol, 2,6-octadien-1-ol, 3,7-dimethyl-(E)-2,6-octadienal, 3,7-dimethylcyclohexanol, and cyclohexanol, 2-methylene-5-(1-methylethenyl) which were reported to have specifically antimicrobial activity. PMID:25389517

Dubey, Debasmita; Patnaik, Rajashree; Ghosh, Goutam; Padhy, Rabindra N.

2014-01-01

240

Identification of Major Histocompatibility Complex-Regulated Body Odorants by Statistical Analysis of a Comparative Gas Chromatography/Mass Spectrometry Experiment  

SciTech Connect

Gas chromatography (GC), combined with mass spectrometry (MS) detection, is a powerful analytical technique that can be used to separate, quantify, and identify volatile compounds in complex mixtures. This paper examines the application of GC-MS in a comparative experiment to identify volatiles that differ in concentration between two groups. A complex mixture might comprise several hundred or even thousands of volatile compounds. Because their number and location in a chromatogram generally are unknown, and because components overlap in populous chromatograms, the statistical problems offer significant challenges beyond traditional two-group screening procedures. We describe a statistical procedure to compare two-dimensional GC-MS profiles between groups, which entails (1) signal processing: baseline correction and peak detection in single ion chromatograms; (2) aligning chromatograms in time; (3) normalizing differences in overall signal intensities; and (4) detecting chromatographic regions that differ between groups. Compared to existing approaches, the proposed method is robust to errors made at earlier stages of analysis, such as missed peaks or slightly misaligned chromatograms. To illustrate the method, we identify differences in GC-MS chromatograms of ether-extracted urine collected from two nearly identical inbred groups of mice, to investigate the relationship between odor and genetics of the major histocompatibility complex.

Willse, Alan R.; Belcher, Ann; Preti, George; Wahl, Jon H.; Thresher, Miranda; Yang, Peter; Yamazaki, Kunio; Beauchamp, Gary

2005-04-15

241

Planar solid phase extraction--a new clean-up concept in multi-residue analysis of pesticides by liquid chromatography-mass spectrometry.  

PubMed

Efficient clean-up is indispensable for preventing matrix effects in multi-residue analysis of pesticides in food by liquid and gas chromatography coupled to mass spectrometry. As a completely new approach, highly automated planar chromatographic tools were applied for powerful clean-up, called high-throughput planar solid phase extraction (HTpSPE). Thin-layer chromatography (TLC) was used to completely separate pesticides from matrix compounds and to focus them into a sharp zone, followed by extraction of the target zone by the TLC-MS interface. HTpSPE resulted in extracts nearly free of interference and free of matrix effects, as shown for seven chemically representative pesticides in four different matrices (apples, cucumbers, red grapes, tomatoes). Regarding the clean-up step, quantification by LC-MS provided mean recovery (against solvent standards) of 90-104% with relative standard deviations of 0.3-4.1% (n=5) for two spiking levels of 0.1 and 0.5 mg/kg. Clean-up of one sample was completed in a manner of minutes, while running numerous samples in parallel at reduced costs, with very low sample and solvent volumes. PMID:21794869

Oellig, Claudia; Schwack, Wolfgang

2011-09-16

242

Comparison and analysis of organochlorine pesticides and hexabromobiphenyls in environmental samples by gas chromatography-electron capture detector and gas chromatography-mass spectrometry.  

PubMed

Two analytical methods, gas chromatography-electron capture detector (GC-ECD) and gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS), were evaluated and compared for the measurement of persistent organic pollutants, specifically for 26 organochlorine pesticides and two hexabromobiphenyls, in atmospheric particulate matter and soil samples. The hypothesis tested was that the coelution of non-target compounds may lead to false positives when analyzed by GC-ECD, and that the overestimation associated with these false positives can be eliminated using GC-NCI-MS. The study showed that both methods had satisfactory linearity and reproducibility for the target compounds. Although the sensitivities of GC-ECD for most of the compounds investigated were higher than those observed with the GC-NCI-MS method, the matrices interference was obvious with GC-ECD. There was indeed an apparently high false-positive rate or overestimate when GC-ECD was used for environmental samples, implying that the GC-ECD method has been used with care and that GC-NCI-MS is generally superior for the analysis of trace amounts of these compounds in environmental samples. Based on these results, the sample extraction and cleanup procedures of the GC-NCI-MS method were optimized for achieving acceptable recoveries and less matrices interference. PMID:24872522

Liu, Yu; Fu, Xiaofang; Tao, Shu; Liu, Liang; Li, Wei; Meng, Bingjun

2015-02-01

243

Use of spermine and thiabendazole as analyte protectants to improve direct analysis of 16 carbamates by gas chromatography-mass spectrometry in green vegetable matrices.  

PubMed

The carbamates are a well-known thermosensible pesticides class, which are highly prone to degradation via fragmentation and/or rearrangement mechanisms leading to a difficult direct gas chromatography (GC) analysis, i.e., without derivatization. In this paper, spermine and thiabendazole both at 1 mg/mL were highlighted as efficient analyte protectants to improve the direct and simultaneous analysis of 16 carbamates both in solvent and green vegetable matrices. These two molecules were compared in mixture or in combination with three well-known efficient analyte protectants 3-ethoxy-1,2-propanediol, D-sorbitol, and L-gulonic acid-gamma-lactone. The potential benefits were investigated in GC hyphenated to mass spectrometry (GC-MS) with two injection modes: programmable temperature vaporizing injector in a solvent split mode (PTV-SSI) and on-column injection (OCI). It was shown that the combined effect of the five protective agents led to the best sensitivity improvement with limits of detection between 0.1-0.4 and 0.03-0.1 microg/kg and limits of quantification between 0.3-1.1 and 0.1-0.5 microg/kg for PTV-SSI and OCI mode, respectively. The correlation coefficients from the analyzed 1-500 microg/kg range were all >0.999 both in the solvent and matrices studied. The recoveries of carbamates from three spiked matrices over five replicates at 20 and 100 microg/kg were in the range 90-107% with relative standard deviation (RSD) equal to 2-7% for PTV-SSI and 92-107% with an RSD equal to 1-6% for OCI. The use of spermine and thiabendazole with other analyte protectants shows very efficient partial or total reduction of breakdown of the most sensitive carbamates such as the N-sulfenylated ones. PMID:19415245

Przybylski, Cédric; Bonnet, Véronique

2009-06-01

244

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

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

Peters, Sonja; Kaal, Erwin; Horsting, Iwan; Janssen, Hans-Gerd

2012-02-24

245

Gas chromatography-mass spectrometry of N-heptafluorobutyryl isobutyl esters of amino acids in the analysis of the kinetics of (/sup 15/N)H/sub 4//sup +/ assimilation in Lemna minor L  

SciTech Connect

Rapid, sensitive, and selective methods for the determination of the /sup 15/N abundance of amino acids in isotopic tracer experiments with plant tissues are described and discussed. Methodology has been directly tested in an analysis of the kinetics of (/sup 15/N)H/sub 4//sup +/ assimilation in Lemna minor L. The techniques utilize gas chromatography-mass spectrometry selected ion monitoring of major fragments containing the N moiety of N-heptafluorobutyryl isobutyl esters of amino acids. The ratio of selected ion pairs at the characteristic retention time of each amino acid derivative can be used to calcuulate /sup 15/N abundance with an accuracy of +/- 1 atom % excess /sup 15/N using samples containing as little as 30 picomoles of individual amino acids. Up to 11 individual amino acid derivatives can be selectively monitored in a single chromatogram of 30 minutes. It is suggested that these techniques will be useful in situations where the small quantities of N available for analysis have hitherto hindered the use of /sup 15/N-labeled precursors.

Rhodes, D.; Myers, A.C.; Jamieson, G.

1981-11-01

246

Variability of matrix effects in liquid and gas chromatography-mass spectrometry analysis of pesticide residues after QuEChERS sample preparation of different food crops.  

PubMed

Gas and liquid chromatography (GC and LC) coupled to mass spectrometry (MS) serve as the most powerful analytical tools commonly used to monitor pesticide residues in food, among other applications. However, both GC-MS and LC-MS are susceptible to matrix effects which can adversely affect quantification depending on the analyte, matrix, sample preparation, instrumentation, and operating conditions. Among the approaches that reduce matrix effects, the most common in pesticide residue applications is matrix-matched calibration because it is relatively inexpensive and simple. Also, it has been shown to work well during method validation when fortified samples are exactly matched with samples used for calibration. However, the quality of matrix-matched results in real-world analyses depends on the consistency of matrix effects among diverse samples. In this study, the variability of matrix effects was measured for 38 representative pesticides in 20 samples each (including different varieties) of rice, orange, apple, and spinach extracted using the "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) method for analysis by LC-MS/MS and low-pressure GC-MS. Using LC-MS/MS, only oranges gave >20% matrix effects for a few pesticides. GC-MS exhibited larger matrix effects, but as in LC-MS/MS, the differences were reasonably consistent among the 20 samples tested. Main conclusions of this study are that for the conditions utilized: (1) matrix-matching was not needed for most pesticides in the simpler food matrices; and (2) for the more complex orange matrix, acceptably accurate quantitative results were achieved by using matrix-matching even with a different sample of the same type. However, full confidence cannot be extended to matrix-matched results, and for consequential applications such as regulatory enforcement, confirmatory analyses using alternate quantitative determinations should also be conducted. PMID:23182936

Kwon, Hyeyoung; Lehotay, Steven J; Geis-Asteggiante, Lucía

2012-12-28

247

Extraction of pesticides, dioxin-like PCBs and PAHs in water based commodities using liquid-liquid microextraction and analysis by gas chromatography-mass spectrometry.  

PubMed

Water based samples such as flavored drinks, juices and drinking water may contain contaminants at ultra trace level belonging to different chemical classes. A novel, simple, low-cost and fast method was developed and validated for trace residue extraction of pesticides, dioxin-like PCBs and PAHs from water and water based samples followed by analysis through gas chromatography (GC) coupled with time-of-flight mass spectrometry (ToFMS). The extraction solvent type, volume; sample volume and other extraction conditions were optimized. This was achieved by extracting 10 mL sample with 250 ?L chloroform by vortexing (1 min, standing time of 2 min) followed by centrifugation (6000 rpm, 5 min). The bottom organic layer (200 ?L) was pipetted out, evaporated to near dryness and reconstituted in 20 ?L of ethyl acetate+cyclohexane (1:9) mixture resulting in an enrichment factor of 400. The recoveries of all compounds were within 76-120% (±10%) with the method detection limit (MDL) ranging from 1 to 250 ng/L depending on the analyte response. The MDLs were 400 times lower than the instrument quantification limits that ranged from 0.4 to 100 ng/mL. The method was further validated in water based drinks (e.g. apple, lemon, pineapple, orange, grape and pomegranate juice). For the juices with suspended pulp, the extraction was carried out with 400 ?L chloroform. The extract was analyzed by GC-ToFMS at both 1D and GC×GC modes to chromatographically separate closely eluting interfering compounds the effect of which could not be minimized otherwise. The resulting peak table was filtered to identify a range of compounds belonging to specific classes viz. polycyclic aromatic hydrocarbons, chlorinated, brominated, and nitro compounds. User developed scripts were employed on the basis of identification of the molecular ion and isotope clusters or other spectral characteristics. The method performed satisfactorily in analyzing both incurred as well as market samples. PMID:21820665

Dasgupta, Soma; Banerjee, Kaushik; Utture, Sagar; Kusari, Parijat; Wagh, Sameer; Dhumal, Kondiba; Kolekar, Sanjay; Adsule, Pandurang G

2011-09-23

248

Online capillary solid-phase microextraction coupled liquid chromatography-mass spectrometry for analysis of chiral secondary alcohol products in yeast catalyzed stereoselective reduction cell culture.  

PubMed

An online solid-phase microextraction coupled liquid chromatography-electrospray ionization-ion trap mass spectrometry was developed for the analysis of trace R- and S-4-phenyl-2-butanol (R- and S-pbol) in salt rich cell culture of Saccharomyces cerevisiae catalyzed stereoselective reduction of 4-pheny-2-butanone (pbone). A Supel-Q PLOT capillary column was used for the extraction and deionized distilled water was used as the extraction mobile phase. The extraction flow rate and extraction time were at 0.1 mL min(-1) and 0.95 min, respectively. The three target analytes, pbone, R-pbol, and S-4-pbol, were desorbed and eluted by the mobile phase of water/methanol/isopropanol (55/25/20, v/v/v) with a flow rate of 0.5 mL min(-1) and analyzed by a chiral column. The mass spectrometric detection of the three target analytes was in positive ion mode with the signal [M+Na](+). The matrix-matched external standard calibration curves with linear concentration range between 0 and 50 ?g mL(-1) were used for quantitative analysis. The linear regression correlation coefficients (r(2)) of the standard calibration curves were between 0.9950 and 0.9961. The yeast mediated reduction was performed with a recation culture of yeast incubation culture/glycerol (70/30, v/v) for 4 days. This biotransformation possessed 82.3% yield and 92.9% S-enantomeric excess. The limit of detection (LOD)/limit of quantification (LOQ) for pbone, R-pbol, and S-pbol was 0.02/0.067, 0.01/0.033, and 0.01/0.033 ?g mL(-1), respectively. The intra-day and inter-day precisions from repeated measurements were 10.8-21.1% and 11.6-18.7%, respectively. The analysis accuracy from spike recovery was 84-91%. PMID:25563398

Cheng, Cheanyeh; Nian, Yu-Chuan

2015-02-01

249

Quantification of veterinary antibiotics (sulfonamides and trimethoprim) in animal manure by liquid chromatography–mass spectrometry  

Microsoft Academic Search

A fast and cost effective method was developed to extract and quantify residues of veterinary antimicrobial agents (antibiotics) in animal manure by liquid–liquid extraction and liquid chromatography–mass spectrometry. The compounds investigated include six sulfonamides, one metabolite, and trimethoprim. The method was performed without sample clean up. Recoveries from spiked manure slurry samples (spike level=1 mg\\/kg) were as follows: sulfaguanidine (52%),

Michel Y. Haller; Stephan R. Muller; Christa S. McArdell; Alfredo C. Alder; Marc J.-F. Suter

2002-01-01

250

An integrated method for spectrum extraction and compound identification from gas chromatography\\/mass spectrometry data  

Microsoft Academic Search

A method is presented for extracting individual component spectra from gas chromatography\\/mass spectrometry (GC\\/MS) data files\\u000a and then using these spectra to identify target compounds by matching spectra in a reference library. It extends a published\\u000a “model peak” approach which uses selected ion chromatograms as models for component shape. On the basis of this shape, individual\\u000a mass spectral peak abundance

S. E. Stein

1999-01-01

251

Evaluation of plasma enzyme activities using gas chromatography–mass spectrometry based steroid signatures  

Microsoft Academic Search

The simultaneous quantification of 65 plasma steroids, including 22 androgens, 15 estrogens, 15 corticoids and 13 progestins, was developed using gas chromatography-mass spectrometry (GC–MS). The extraction efficiency of the catechol estrogens was improved by the addition of l-ascorbic acid in several steps. All steroids, as their trimethylsilyl derivatives, were well separated with good peak shapes within a 50min run. The

Young Wan Ha; Ju-Yeon Moon; Hyun-Jin Jung; Bong Chul Chung; Man Ho Choi

2009-01-01

252

Determination of hydroxyl radicals using salicylate as a trapping agent by gas chromatography-mass spectrometry  

Microsoft Academic Search

Objectives: To establish a sensitive method for measuring hydroxyl radical formation in biological systems using salicylate as probe.Methods: Salicylate hydroxylation products and related aromatic compounds were extracted and converted to trimethylsilyl (TMS) derivatives. The derivatives were analyzed by gas chromatography-mass spectrometry (GC-MS). Quantitation was achieved by selected-ion-recording (SIR) with benzoic acid (ring-D5) as an internal standard.Results: All compounds were well

Xiaoping Luo; Denis C. Lehotay

1997-01-01

253

Detection of Quaternary Ammonium Drugs in Equine Urine by Liquid Chromatography-Mass Spectrometry  

Microsoft Academic Search

Quaternary ammonium drugs are anticholinergic agents and some of which have been known to be abused in equine sports. A general screening method for this class of drugs in equine urine by liquid chromatography-mass spectrometry (LC-MS) has not been reported. The paper describes an efficient LC-MS-MS method for the simultaneous detection and confirmation of twenty quaternary ammonium drugs at low

K. C. H. Yiu; E. N. M. Ho; T. S. M. Wan

2004-01-01

254

Characterization of gamma irradiated petrolatum eye ointment base by headspace–gas chromatography–mass spectrometry  

Microsoft Academic Search

The effects of gamma irradiation on petrolatum eye ointment base (EOB) and its ingredients (white petrolatum, liquid paraffin, and wool fat) were studied at different irradiation doses. Forty-one volatile radiolysis products were detected and identified by a combined system of headspace–gas chromatography–mass spectrometry (HS–GC–MS). The characteristics of the radiolysis products and the degradation pathway were discussed in each case, respectively.

Lan Hong; Hans Altorfer

2002-01-01

255

Pesticide residue determination in fruit and vegetables by liquid chromatography–mass spectrometry  

Microsoft Academic Search

An overview is given of pesticide residue determination in fruit and vegetables by liquid chromatography–mass spectrometry (LC–MS). Emphasis is placed on the thermospray, particle beam and atmospheric pressure ionization interfaces including advantages and drawbacks and typical detection limits. The capacity of each interface to provide useful data for identification\\/confirmation of analytes and the possibility of obtaining structural information for the

Y Picó; J. C Moltó; J Mañes

2000-01-01

256

Determination of glyphosate, glyphosate metabolites, and glufosinate in human serum by gas chromatography–mass spectrometry  

Microsoft Academic Search

This paper describes an assay for the determination of glyphosate (GLYP), glyphosate metabolites [(aminomethyl) phosphonic acid] (AMPA), and glufosinate (GLUF) in human serum. After protein precipitation using acetonitrile and solid-phase extraction, serum samples were derivatized and analyzed by gas chromatography–mass spectrometry (GC–MS). The assay was linear over a concentration range of 3–100.0?g\\/ml for GLYP, AMPA, and GLUF. The overall recoveries

Megumi Motojyuku; Takeshi Saito; Kazuki Akieda; Hiroyuki Otsuka; Isotoshi Yamamoto; Sadaki Inokuchi

2008-01-01

257

Chemical characterization of odorous gases at a landfill site by gas chromatography–mass spectrometry  

Microsoft Academic Search

The composition of odorous gases emitted from a municipal landfill in the city of Izmir, Turkey was investigated using gas chromatography–mass spectrometry, and these data were examined in relation with the odor concentrations. Several volatile organic compounds (VOCs) were identified and quantified at five sampling sites in May and September 2005. Detected VOCs were monoaromatics (0.09–47.42?gm?3), halogenated compounds (0.001–62.91?gm?3), aldehydes

Faruk Dincer; Mustafa Odabasi; Aysen Muezzinoglu

2006-01-01

258

Rapid and sensitive liquid chromatography–mass spectrometry method for determination of ropinirole in human plasma  

Microsoft Academic Search

A rapid and robust liquid chromatography–mass spectrometry (LC–MS\\/MS) method was developed for non-ergoline dopamine D2-receptor agonist, ropinirole in human plasma using Es-citalopram oxalate as an internal standard. The method involves solid phase extraction from plasma, reversed-phase simple isocratic chromatographic conditions and mass spectrometric detection that enables a detection limit at picogram levels. The proposed method was validated with linear range

Jignesh Bhatt; Arvind Jangid; Raghavendra Shetty; Bhavin Shah; Sandeep Kambli; Gunta Subbaiah; Sadhana Singh

2006-01-01

259

Determination of cocaine in postmortem human liver exposed to overdose. Application of an innovative and efficient extraction/clean up procedure and gas chromatography-mass spectrometry analysis.  

PubMed

A simple and efficient method was developed for the determination of cocaine in post-mortem samples of human liver via solid-liquid extraction with low temperature partitioning (SLE-LTP) and analysis by gas chromatography coupled to mass spectrometry (GC-MS). The extraction procedure was optimized by evaluating the influence of the following variables: pH of the extract, volume and composition of the extractor solvent, addition of a sorbent material (PSA: primary-secondary amine) and NaCl to clean up and increase the ionic strength of the extract. A bovine liver sample that was free of cocaine was used as a blank for the optimization of the SLE-LTP extraction procedure. The highest recovery was obtained when crushed bovine liver (2g) was treated with 2mL of ultrapure water plus 8mL of acetonitrile at physiological pH (7.4). The results also indicated no need for using PSA and NaCl. The complete analytical procedure was validated for the following figures of merit: selectivity, lower limit of quantification (LLOQ), calibration curve, recovery, precision and accuracy (for within-run and between-run experiments), matrix effect, dilution integrity and stability. The within-run and between-run precision (at four levels) varied from 2.1% to 9.4% and from 4.0% to 17.0%, respectively. A maximum deviation of 11.62% for the within-run and between-run accuracies in relation to the nominal concentrations was observed. Moreover, the LLOQ value for cocaine was 50.0ngg(-1) whereas no significant effects were noticed in the assays of dilution integrity and stability. To assess its overall performance, the optimized method was applied to the analysis of eight human liver samples collected from individuals who died due to the abusive consumption of cocaine. Due to the existence of a significant matrix effect, a blank human liver was used to construct a matrix-matched analytical curve. The concentrations of cocaine found in these samples ranged from 333.5 to 5969ngg(-1). PMID:23972460

Magalhães, Elisângela Jaqueline; Ribeiro de Queiroz, Maria Eliana Lopes; Penido, Marcus Luiz de Oliveira; Paiva, Marco Antônio Ribeiro; Teodoro, Janaína Aparecida Reis; Augusti, Rodinei; Nascentes, Clésia Cristina

2013-09-27

260

Determination of N-nitrosodiethanolamine in cosmetic products by headspace solid phase microextraction using a novel aluminum hydroxide grafted fused silica fiber followed by gas chromatography-mass spectrometry analysis.  

PubMed

A method based on headspace solid phase microextraction with a new fiber, coupled with gas chromatography-mass spectrometry was developed for the determination of NDELA in cosmetic samples. The fiber provides Lewis acid-base interaction between its surface and analyte functional groups. The fiber was prepared by grafting aluminum tri-tert-butoxide on the surface of a fused silica. The optimization of SPME conditions showed that NDELA can be most effectively extracted at 70°C, in 15 min, with a sample volume of 0.5 (Vs/Vt), stirring rate of 150 rpm, desorption time of 5 min, desorption temperature of 260°C and at 12.5% (w/w) concentration of NaCl. Under the optimized conditions, LOD of 1 ?g Kg(-1) and a calibration curve with correlation coefficients greater than 0.9897 and a linearity range from 6 to 10000 ?g Kg(-1) were obtained. The intra-day and inter-day precision and accuracy were evaluated at four concentration levels. All of the values for accuracy and precision were lower than the acceptable limit of 15%. The fiber to fiber repeatability was 8.7%. The method was applied for the analysis of real samples including hair shampoo, body shampoo, dishwashing liquid and hand washing liquid. Relative recoveries were achieved in the range of 95-99%. PMID:23598029

Davarani, Saied Saeed Hosseiny; Masoomi, Leila; Banitaba, Mohammad Hossein; Zhad, Hamid Reza Lotfi Zadeh; Sadeghi, Omid; Samiei, Azam

2013-02-15

261

Methods of analysis and quality-assurance practices of the U.S. Geological Survey organic laboratory, Sacramento, California; determination of pesticides in water by solid-phase extraction and capillary-column gas chromatography/mass spectrometry  

USGS Publications Warehouse

Analytical method and quality-assurance practices were developed for a study of the fate and transport of pesticides in the Sacramento-San Joaquin Delta and the Sacramento and San Joaquin River. Water samples were filtered to remove suspended parti- culate matter and pumped through C-8 solid-phase extraction cartridges to extract the pesticides. The cartridges were dried with carbon dioxide, and the pesticides were eluted with three 2-milliliter aliquots of hexane:diethyl ether (1:1). The eluants were analyzed using capillary-column gas chromatography/mass spectrometry in full-scan mode. Method detection limits for analytes determined per 1,500-milliliter samples ranged from 0.006 to 0.047 microgram per liter. Recoveries ranged from 47 to 89 percent for 12 pesticides in organic-free, Sacramento River and San Joaquin River water samples fortified at 0.05 and 0.26 microgram per liter. The method was modified to improve the pesticide recovery by reducing the sample volume to 1,000 milliliters. Internal standards were added to improve quantitative precision and accuracy. The analysis also was expanded to include a total of 21 pesticides. The method detection limits for 1,000-milliliter samples ranged from 0.022 to 0.129 microgram per liter. Recoveries ranged from 38 to 128 percent for 21 pesticides in organic-free, Sacramento River and San Joaquin River water samples fortified at 0.10 and 0.75 microgram per liter.

Crepeau, Kathryn L.; Domagalski, Joseph L.; Kuivila, Kathryn M.

1994-01-01

262

Methods of analysis by the U.S. Geological Survey Organic Geochemistry Research Group; determination of chloroacetanilide herbicide metabolites in water using high-performance liquid chromatography-diode array detection and high-performance liquid chromatography/mass spectrometry  

USGS Publications Warehouse

Analytical methods using high-performance liquid chromatography-diode array detection (HPLC-DAD) and high-performance liquid chromatography/mass spectrometry (HPLC/MS) were developed for the analysis of the following chloroacetanilide herbicide metabolites in water: acetochlor ethanesulfonic acid (ESA), acetochlor oxanilic acid (OXA), alachlor ESA, alachlor OXA, metolachlor ESA, and metolachlor OXA. Good precision and accuracy were demonstrated for both the HPLC-DAD and HPLC/MS methods in reagent water, surface water, and ground water. The mean HPLC-DAD recoveries of the chloroacetanilide herbicide metabolites from water samples spiked at 0.25, 0.50, and 2.0 mg/L (micrograms per liter) ranged from 84 to 112 percent, with relative standard deviations of 18 percent or less. The mean HPLC/MS recoveries of the metabolites from water samples spiked at 0.05, 0.20, and 2.0 mg/L ranged from 81 to 125 percent, with relative standard deviations of 20 percent or less. The limit of quantitation (LOQ) for all metabolites using the HPLC-DAD method was 0.20 mg/L, whereas the LOQ using the HPLC/MS method was 0.05 mg/L. These metabolite-determination methods are valuable for acquiring information about water quality and the fate and transport of the parent chloroacetanilide herbicides in water.

Zimmerman, L.R.; Hostetler, K.A.; Thurman, E.M.

2000-01-01

263

Advanced Capillary Liquid Chromatography-Mass Spectrometry for Proteomics  

SciTech Connect

The liquid chromatography (LC)-mass spectrometric (MS) analysis of peptides has become a routine method for proteomics – the study of the entire complement of proteins e.g., expressed by a cell under a specific set of conditions at a specific time. Mixtures of peptides, such as those generated from enzymatic (e.g., trypsin) digestion of globally recovered proteins (i.e. a proteome), are typically very complex and >100,000 different molecular species may be observable using MS detection [1]. LC separations implemented prior to MS for broad protein identification have three major roles: 1) to isolate individual components or reduce complexity as much as possible, 2) to increase sensitivity by concentrating the components into narrow zones prior to MS, and 3) to eliminate or displace interfering species (e.g., salts and polymers) that may be present in proteomics samples. A desired quality of LC separation can be achieved from the use of either multiple steps of moderate quality separations, or fewer steps of high power separations. The former approach is generally more easily accessible for very high quality separations due to the variety of commercialized LC platforms available, while the latter still often requires considerable developmental efforts (for both columns and instrumentation). In addition to proteomics data quality, other differences between these two approaches include proteomics analysis time and sample consumption (and subsequent analysis costs), as well as direct impact on potential proteomics applications that have special requirements in terms of analysis coverage, sample size, dynamic range, sensitivity, and throughput.

Shen, Yufeng; Page, Jason S.; Smith, Richard D.

2009-02-23

264

Variability of matrix effects in liquid and gas chromatography - mass spectrometry analysis of pesticide residues after QuEChERS sample preparation of different food crops  

Technology Transfer Automated Retrieval System (TEKTRAN)

Gas and liquid chromatography (GC and LC) coupled to sophisticated mass spectrometry (MS) instruments are among the most powerful analytical tools currently available to monitor pesticide residues in food, among other applications. However, both GC-MS and LC-MS are susceptible to matrix effects whi...

265

Factors That Contribute to Assay Variation in Quantitative Analysis of Sex Steroid Hormones Using Liquid and Gas Chromatography-Mass Spectrometry  

ERIC Educational Resources Information Center

The list of physiological events in which sex steroids play a role continues to increase. To decipher the roles that sex steroids play in any condition requires high quality cohorts of samples and assays that provide highly accurate quantitative measures. Liquid and gas chromatography coupled with mass spectrometry (LC-MS and GC-MS) have…

Xu, Xia; Veenstra, Timothy D.

2012-01-01

266

Isotope Ratio Monitoring Gas Chromatography Mass Spectrometry (IRM-GCMS)  

NASA Technical Reports Server (NTRS)

On Earth, the C-13 content of organic compounds is depleted by roughly 13 to 23 permil from atmospheric carbon dioxide. This difference is largely due to isotope effects associated with the fixation of inorganic carbon by photosynthetic organisms. If life once existed on Mars, then it is reasonable to expect to observe a similar fractionation. Although the strongly oxidizing conditions on the surface of Mars make preservation of ancient organic material unlikely, carbon-isotope evidence for the existence of life on Mars may still be preserved. Carbon depleted in C-13 could be preserved either in organic compounds within buried sediments, or in carbonate minerals produced by the oxidation of organic material. A technique is introduced for rapid and precise measurement of the C-13 contents of individual organic compounds. A gas chromatograph is coupled to an isotope-ratio mass spectrometer through a combustion interface, enabling on-line isotopic analysis of isolated compounds. The isotope ratios are determined by integration of ion currents over the course of each chromatographic peak. Software incorporates automatic peak determination, corrections for background, and deconvolution of overlapped peaks. Overall performance of the instrument was evaluated by the analysis of a mixture of high purity n-alkanes of know isotopic composition. Isotopic values measured via IRM-GCMS averaged withing 0.55 permil of their conventionally measured values.

Freeman, K. H.; Ricci, S. A.; Studley, A.; Hayes, J. M.

1989-01-01

267

Development of a technique for mercury speciation and quantification using gas chromatography/mass spectrometry  

SciTech Connect

One element of concern to DOE is mercury. Mercury was used extensively at the DOE facilities in Oak Ridge, Tennessee from 1950 to 1963 in the process of making lithium deuteride, a component of nuclear weapons. Although both the inorganic and organometallic forms of mercury are toxic to humans, the organic compounds are often more toxic. Since the toxicity of mercury is a function of its chemical form, an understanding of the interactions between commercially discharged mercury, naturally occurring mercury, and the environment in which they are present is vital. In this report, the authors have been investigating gas chromatography/mass spectrometry (GC/MS) for the analysis of both the organometallic and inorganic forms of mercury in the same environmental sample (e.g., solutions, soils, and sludges). Although gas chromatography is the classical technique for analyzing organic molecules, (e.g., organometallic compounds) little has been done on the analysis of inorganic compounds. In a previous publication, the authors described how a solid phase microextraction (SPME) fiber could be used to sample organomercurials from aqueous samples. An alkylation reaction was then carried out to transform chemically mercury nitrate into dimethylmercury; subsequent GC/MS analysis of this compound permitted quantification of the inorganic constituent. Subsequently, several different alkylation reagents have been synthesized that methylate any inorganic mercury compound to methylmercury iodide. Here, the authors report results on alkylation reaction time and the effect of pH on the population of the product.

Barshick, S.A.; Barshick, C.M.; Britt, P.F.; Vance, M.A.; Duckworth, D.C.

1997-07-01

268

Identification and differentiation of methcathinone analogs by gas chromatography-mass spectrometry.  

PubMed

To overcome a number of challenges involved in analyzing methcathinone (MC) analogues, we performed gas chromatography-mass spectrometry (GC-MS) analysis, including sample preparation, of nine MC analogues?-?4-methylmethcathinone, three positional isomers of fluoromethcathinones, 4-methoxymethcathinone, N-ethylcathinone, N,N-dimethylcathinone, buphedrone, and pentedrone. The MC analogues underwent dehydrogenation when the free bases were analyzed using splitless injection. Most of this thermal degradation was prevented using split injection. This indicated that a shorter residence time in the hot injector prevented decomposition. Uniquely, 2-fluoromethcathinone degraded to another product in a process that could not be prevented by the split injection. Replacing the liner with a new, clean one was also effective in preventing thermal degradation. Most of the analytes showed a substantial loss (>30%) when the free base solution in ethyl acetate was evaporated under a nitrogen stream. Adding a small amount of dimethylformamide as a solvent keeper had a noticeable effect, but it did not completely prevent the loss. Three positional isomers of fluoromethcathinones were separated with baseline resolution by heptafluorobutyrylation with a slow column heating rate (8?°C/min) using a non-polar DB-5?ms capillary column. These results will be useful for the forensic analysis of MC analogues in confiscated materials. PMID:23161815

Tsujikawa, Kenji; Mikuma, Toshiyasu; Kuwayama, Kenji; Miyaguchi, Hajime; Kanamori, Tatsuyuki; Iwata, Yuko T; Inoue, Hiroyuki

2013-08-01

269

Valid internal standard technique for arson detection based on gas chromatography-mass spectrometry.  

PubMed

The most popular procedures for the detection of residues of accelerants in fire debris are the ones published by the American Society for Testing and Materials (ASTM E1412-07 and E1618-10). The most critical stages of these tests are the conservation of fire debris from the sampling to the laboratory, the extraction of residues of accelerants from the debris to the activated charcoal strips (ACS) and from those to the final solvent, as well as the analysis of sample extract by gas chromatography-mass spectrometry (GC-MS) and the interpretation of the instrumental signal. This work proposes a strategy for checking the quality of the sample conservation, the accelerant residues transference to final solvent and GC-MS analysis, using internal standard additions. It is used internal standards ranging from a highly volatile compound for checking debris conservation to low volatile compound for checking GC-MS repeatability. The developed quality control (QC) parameters are not affected by GC-MS sensitivity variation and, specifically, the GC-MS performance control is not affected by ACS adsorption saturation that may mask test performance deviations. The proposed QC procedure proved to be adequate to check GC-MS repeatability, ACS extraction and sample conservation since: (1) standard additions are affected by negligible uncertainty and (2) observed dispersion of QC parameters are fit for its intended use. PMID:22920302

Salgueiro, Pedro A S; Borges, Carlos M F; Bettencourt da Silva, Ricardo J N

2012-09-28

270

Derivatization followed by gas chromatography-mass spectrometry for quantification of ethyl carbamate in alcoholic beverages.  

PubMed

A sensitive and rapid analytical methodology based on derivatization followed by gas chromatography-mass spectrometry (GC-MS) was developed for the quantitative determination of the toxic contaminant ethyl carbamate (EC, urethane, C(2)H(5)OCONH(2)) in alcoholic samples. EC was extracted using liquid-liquid extraction technique, and then silylated with bis-(trimethylsilyl)trifluoroacetamide, analysed finally by GC-MS. The isopropyl carbamate was used as the internal standard for quantitative analysis of EC in alcoholic samples. In this work, the sample extraction and derivatization reaction conditions were investigated, and the optimal extraction conditions obtained were: pH 9 and solvent of ethyl acetate, and the derivatization conditions were: derivatization reaction temperature of 80°C and time duration of 30 min. With the optimal conditions, the method validations were also studied. In the validation studies, EC exhibited good linearity with a regression coefficient of 0.9999. The limit of detection and limit of quantification were 0.30 and 5.0 ?g/kg, respectively. The precision was less than 8.4%. Finally, the proposed technique was successfully applied to the analysis of EC in 35 kinds of alcoholic samples. The experimental results have demonstrated that the proposed technique is a fast, reliable and low-cost method for determination of EC in alcoholic samples. PMID:22383421

Xu, Xuejiao; Gao, Yihan; Cao, Xiujun; Wang, Xiang; Song, Guoxin; Zhao, Jianfeng; Hu, Yaoming

2012-04-01

271

Quantification of amino acid ionic liquids using liquid chromatography-mass spectrometry.  

PubMed

Amino acid ionic liquids (AAILs) containing imidazolium cations and amino acid (AA) anions, were synthesized and applied as task-specific ionic liquids. A sensitive and fast liquid chromatography-mass spectrometry (LC-MS) method was established for the quantitative analysis of 20 AAILs. Using ion pairing-reversed phase liquid chromatography technique, heptafluorobutyric acid was used as ion-pairing reagent to increase the retention of AAILs. Based on the zwitterionity of amino acid, this method was proposed to determine both the cation and the anion of AAILs simultaneously. The limit of detection of this method is down to 1-15ng/mL and the analysis time is less than 15min. According to the analytical data of seven selected AAILs, we found that the content of amino acid anion is always lower than that of butyl methyl imidazolium cation in AAILs. Moreover, the molar ratio of imidazolium cation to amino acid anion is dependent on the chemical property of the amino acid. These results supplied useful information on the interaction of imidazolium cation with acidic, basic, neutral and non-polar amino acids in AAILs. PMID:18790488

Tang, Fei; Wu, Kangkang; Nie, Zhou; Ding, Li; Liu, Qian; Yuan, Jinbin; Guo, Manli; Yao, Shouzhuo

2008-10-24

272

Characterization of volatile organic compounds by thermal desorption/gas chromatography/mass spectrometry  

SciTech Connect

Carbonaceous triple sorbent traps (TSTs) have been widely used to collect and concentrate volatile organic compounds (VOCs) in vapor phase samples for subsequent GC/MS analysis. Recently, this laboratory has been involved in sampling and analyzing VOCs collected from various emission sources, including headspace samples from underground storage tanks at the Department of Energy`s Hanford site, in Richland, Washington. In order to evaluate the sampling adequacy and to assess any health-related impact based on the analysis results, a validated method must be employed. Therefore, the main objective of this study was to develop a methology for thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS) determination of VOCs in the vapor phase samples collected on Carbotrap C/Carbotrap/Carbosieve S III triple sorbent traps. Techniques used in method validation included VOC standard generation, thermal desorption efficiency, reproducibility of spiking on and recovery from TST, use of internal standards, detection limits determination, linearity and reproducibility of calibration.

Ma, Cheng-Yu; Skeen, J.T.; Dindal, A.B. [Oak Ridge National Lab., TN (United States)] [and others

1995-12-31

273

Identification of floral scent in chrysanthemum cultivars and wild relatives by gas chromatography-mass spectrometry.  

PubMed

The objective of this study was to identify the major volatile compounds and their relative concentrations in flowers of different chrysanthemum cultivars and their wild relatives. The volatile organic components of fresh flowers were analyzed using a headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry. In total, 193 volatile organic components were detected; the major scent components were monoterpenoids and oxygenated monoterpenoids, which accounted for 68.59%-99.93% of the total volatiles in all tested materials except for Chrysanthemum indicum collected from Huangshan, in which they accounted for only 37.45% of total volatiles. The major volatile compounds were camphor, ?-pinene, chrysanthenone, safranal, myrcene, eucalyptol, 2,4,5,6,7,7ab-hexahydro-1H-indene, verbenone, ?-phellandrene and camphene. In a hierarchical cluster analysis, 39 accessions of Chrysanthemum and its relatives formed six clusters based on their floral volatile compounds. In a principal component analysis, only spider type flowers were located closely on the score plot. The results of this study provide a basis for breeding chrysanthemum cultivars which desirable floral scents. PMID:25816078

Sun, Hainan; Zhang, Ting; Fan, Qingqing; Qi, Xiangyu; Zhang, Fei; Fang, Weimin; Jiang, Jiafu; Chen, Fadi; Chen, Sumei

2015-01-01

274

Metabolomics research on the hepatoprotective effect of Angelica sinensis polysaccharides through gas chromatography-mass spectrometry.  

PubMed

Angelica sinensis polysaccharides (ASP) have an established hepatoprotective effect, but the mechanism for this effect remains unclear. A novel approach using biochemical parameters coupled with metabolomics based on gas chromatography-mass spectrometry (GC-MS) and chemometrics was established in this study to explain the hepatoprotective effect mechanism of ASP. The superoxide dismutase activity, malonaldehyde content, alanine aminotransferase, aspartate aminotransferase, and ?-glutamyl transpeptidase in plasma were measured. Pathological changes in the liver were observed. Plasma and liver homogenate obtained from mice were analyzed using GC-MS. Distinct changes in metabolite patterns in the plasma and liver homogenate after being induced by carbon tetrachloride and drug intervention were observed using principal component analysis (PCA) and partial least squares-discriminate analysis (PLS-DA). Potential biomarkers were found using PLS-DA and T-test. The results of the pathological changes observed in the liver, the biochemical parameters in plasma, and the metabolomics of the plasma and liver homogenate all showed that liver injury was successfully reproduced, ASP exhibited hepatoprotective effect, and the medium dose of ASP exhibited the best. Nine endogenous metabolites in the liver homogenate and ten endogenous metabolites in the plasma were all considered as potential biomarkers. They were considered to be in response to hepatoprotective effects of ASP involved in the amino acids metabolism, energy metabolism, and lipids metabolism. Therefore metabolomics is a valuable tool in measuring the efficacy and mechanisms of action of traditional Chinese medicines. PMID:25464094

Ji, Peng; Wei, Yanming; Sun, Hongguo; Xue, Wenxin; Hua, Yongli; Li, Pengling; Zhang, Wenquan; Zhang, Ling; Zhao, Haifu; Li, Jinxia

2014-10-18

275

Determination of leachable components from four commercial dental composites by gas and liquid chromatography\\/mass spectrometry  

Microsoft Academic Search

Objectives: The purpose of our study was to determine the quality and quantity of leachable residual (co)monomers and additives eluted from various commercial dental composite resins after polymerization.Methods: Polymerized specimens from four universal hybrid-type composite resins were eluted for 3 days with methanol resp. water. Then all extracts were analysed by gas chromatography\\/mass spectrometry or liquid chromatography\\/mass spectrometry using a

W. Spahl; H. Budzikiewicz; W. Geurtsen

1998-01-01

276

Identification of two Thormählen-positive compounds from melanotic urine by gas chromatography-mass spectrometry.  

PubMed

The isolation of two Thormählen-positive compounds from the urine of a patient with malignant melanoma and the elucidation of their structure by gas chromatography-mass spectometry is described. The compounds were isolated using a poly-N-vinylpyrrolidone column and separated by preparative thin-layer chromatography. After elution they were analyzed by gas chromatography and gas chromatography-mass spectrometry as their trimethylsilyl derivatives and after hydrolysis also as their tert.-butyldimethylsilyl derivatives. The results showed the main Thormählen-positive compound A to be the glucuronide of 5-hydroxy-6-methoxyindole, whereas the minor compound AX appeared to be the glucuronide of its isomer 6-hydroxy-5-methoxyindole. PMID:7228942

Pavel, S; Muskiet, F A; Nagel, G T; Schwippelová, Z; Duchon, J

1981-03-13

277

Analysis of potential migrants from plastic materials in milk by liquid chromatography-mass spectrometry with liquid-liquid extraction and low-temperature purification.  

PubMed

A simple and fast analytical method was developed for the determination of six UV stabilizers (Cyasorb UV-1164, Tinuvin P, Tinuvin 234, Tinuvin 326, Tinuvin 327, and Tinuvin 1577) and five antioxidants (Irgafos 168, Irganox 1010, Irganox 3114, Irganox 3790, and Irganox 565) in milk. For sample preparation liquid-liquid extraction with low-temperature purification combined with centrifugation was used to remove fats, proteins, and sugars. After the cleanup step, the sample was analyzed with high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS). External standard and matrix calibrations were tested. External calibration proved to be acceptable for Tinuvin P, Tinuvin 234, Tinuvin 326, Tinuvin 327, Irganox 3114, and Irganox 3790. The method was successfully validated with matrix calibration for all compounds. Method detection limits were between 0.25 and 10 ?g/kg. Accuracies ranged from 93 to 109%, and intraday precisions were <13%. PMID:25251884

Bodai, Zsolt; Szabó, Bálint Sámuel; Novák, Márton; Hámori, Susanne; Nyiri, Zoltán; Rikker, Tamás; Eke, Zsuzsanna

2014-10-15

278

Determination of Morphine and Codeine in Human Urine by Gas Chromatography-Mass Spectrometry  

PubMed Central

A sensitive and selective gas chromatography-mass spectrometry (GC-MS) method was developed and validated for the determination of morphine and codeine in human urine. The GC-MS conditions were developed. The analysis was carried out on a HP-1MS column (30?m × 0.25?mm, 0.25??m) with temperature programming, and Helium was used as the carrier gas with a flow rate of 1.0?mL/min. Selected ion monitoring (SIM) mode was used to quantify morphine and codeine. The derivation solvent, temperature, and time were optimized. A mixed solvent of propionic anhydride and pyridine (5?:?2) was finally used for the derivation at 80°C for 3?min. Linear calibration curves were obtained in the concentration range of 25–2000.0?ng/mL, with a lower limit of quantification of 25?ng/mL. The intra- and interday precision (RSD) values were below 13%, and the accuracy was in the range 87.2–108.5%. This developed method was successfully used for the determination of morphine and codeine in human urine for forensic identification study. PMID:24222889

Zhang, Xiaoqian; Cao, Gaozhong; Hu, Guoxin

2013-01-01

279

Multiplicative effects model with internal standard in mobile phase for quantitative liquid chromatography-mass spectrometry.  

PubMed

Liquid chromatography-mass spectrometry assays suffer from signal instability caused by the gradual fouling of the ion source, vacuum instability, aging of the ion multiplier, etc. To address this issue, in this contribution, an internal standard was added into the mobile phase. The internal standard was therefore ionized and detected together with the analytes of interest by the mass spectrometer to ensure that variations in measurement conditions and/or instrument have similar effects on the signal contributions of both the analytes of interest and the internal standard. Subsequently, based on the unique strategy of adding internal standard in mobile phase, a multiplicative effects model was developed for quantitative LC-MS assays and tested on a proof of concept model system: the determination of amino acids in water by LC-MS. The experimental results demonstrated that the proposed method could efficiently mitigate the detrimental effects of continuous signal variation, and achieved quantitative results with average relative predictive error values in the range of 8.0-15.0%, which were much more accurate than the corresponding results of conventional internal standard method based on the peak height ratio and partial least squares method (their average relative predictive error values were as high as 66.3% and 64.8%, respectively). Therefore, it is expected that the proposed method can be developed and extended in quantitative LC-MS analysis of more complex systems. PMID:24840455

Song, Mi; Chen, Zeng-Ping; Chen, Yao; Jin, Jing-Wen

2014-07-01

280

Quantification of veterinary antibiotics (sulfonamides and trimethoprim) in animal manure by liquid chromatography-mass spectrometry.  

PubMed

A fast and cost effective method was developed to extract and quantify residues of veterinary antimicrobial agents (antibiotics) in animal manure by liquid-liquid extraction and liquid chromatography-mass spectrometry. The compounds investigated include six sulfonamides, one metabolite, and trimethoprim. The method was performed without sample clean up. Recoveries from spiked manure slurry samples (spike level = 1 mg/kg) were as follows: sulfaguanidine (52%), sulfadiazine (47%), sulfathiazole (64%), sulfamethazine (89%), its metabolite N4-acetyl-sulfamethazine (88%), sulfamethoxazole (84%), sulfadimethoxine (51%), and trimethoprim (64%). Relative standard deviations of the recoveries were less than 5% within the same day and less than 20% between days. The limit of quantification was below 0.1 mg/kg liquid manure slurry for all compounds and calibration curves obtained from extracts of spiked samples were linear up to a level of 5 mg/kg liquid manure, except for trimethoprim (0.01-0.5 mg/kg). Analysis of six grab samples taken in Switzerland from manure pits on farms where medicinal feed had been applied revealed total sulfonamide concentrations of up to 20 mg/kg liquid manure. PMID:12064522

Haller, Michel Y; Müller, Stephan R; McArdell, Christa S; Alder, Alfredo C; Suter, Marc J F

2002-04-01

281

Baseline correction method using an orthogonal basis for gas chromatography/mass spectrometry data.  

PubMed

A baseline correction method that uses basis set projection to estimate spectral backgrounds has been developed and applied to gas chromatography/mass spectrometry (GC/MS) data. An orthogonal basis was constructed using singular value decomposition (SVD) for each GC/MS two-way data object from a set of baseline mass spectra. A novel aspect of this baseline correction method is the regularization parameter that prevents overfitting that may produce negative peaks in the corrected mass spectra or ion chromatograms. The number of components in the basis, the regularization parameter, and the mass spectral range from which the spectra were sampled to construct the basis were optimized so that the projected difference resolution (PDR) or signal-to-noise ratio (SNR) was maximized. PDR is a metric similar to chromatographic resolution that indicates the separation of classes in a multivariate data space. This new baseline correction method was evaluated with two synthetic data sets and a real GC/MS data set. The prediction accuracies obtained by using the fuzzy rule-building expert system (FuRES) and partial least-squares-discriminant analysis (PLS-DA) as classifiers were compared and validated through bootstrapped Latin partition (BLP) between data before and after baseline correction. The results indicate that baseline correction of the two-way GC/MS data using the proposed methods resulted in a significant increase in average PDR values and prediction accuracies. PMID:21823628

Xu, Zhanfeng; Sun, Xiaobo; Harrington, Peter de B

2011-10-01

282

Identification and differentiation of dragon's blood in works of art using gas chromatography/mass spectrometry.  

PubMed

Dragon's blood is a common but non-specific name for red-coloured resins that are produced by various plants, particularly exudations from plant species belonging to the genera Dracaena and Daemonorops. Although dragon's blood is mentioned in historic sources as a colourant, it has hardly ever been identified in real artworks. This paper reports the identification and discrimination of dragon's blood produced by Dracaena cinnabari, Dracaena draco as well as Daemonorops draco and Daemonorops micracantha by means of gas chromatography/mass spectrometry (GC/MS) within the context of a routine analysis of binding media used in works of art. The detection of specific flavonoid marker compounds in both underivatised and methylated methanol extracts provided the first evidence for the use of dragon's blood from all four species in various works of art from the fifteenth to nineteenth centuries. Dragon's blood was mainly used as a red colourant in gold lacquers as well as translucent glazes and paints, e.g. in reverse-glass paintings (Hinterglasmalerei). PMID:20349349

Baumer, Ursula; Dietemann, Patrick

2010-06-01

283

Profiling of Serum Metabolites in Canine Lymphoma Using Gas Chromatography Mass Spectrometry  

PubMed Central

ABSTRACT Canine lymphoma is a common cancer that has high rates of complete remission with combination chemotherapy. However, the duration of remission varies based on multiple factors, and there is a need to develop a method for early detection of recurrence. In this study, we compared the metabolites profiles in serum from 21 dogs with lymphoma and 13 healthy dogs using gas chromatography mass spectrometry (GC-MS). The lymphoma group was separated from the control group in an orthogonal projection to latent structure with discriminant analysis (OPLS-DA) plot using ions of m/z 100–600, indicating that the metabolites profiles in lymphoma cases differed from those in healthy dogs. The lymphoma group was also separated from the control group on OPLS-DA plot using 29 metabolites identified in all serum samples. Significant differences were found for 16 of these metabolites with higher levels in the lymphoma group for 15 of the metabolites and lower levels for inositol. An OPLS-DA plot showed separation of the lymphoma and healthy groups using these 16 metabolites only. These results indicate that metabolites profile with GC-MS may be a useful tool for detection of potential biomarker and diagnosis of canine lymphoma. PMID:25131950

TAMAI, Reo; FURUYA, Masaru; HATOYA, Shingo; AKIYOSHI, Hideo; YAMAMOTO, Ryohei; KOMORI, Yoshiaki; YOKOI, Shin-ichi; TANI, Kenichiro; HIRANO, Yuji; KOMORI, Masayuki; TAKENAKA, Shigeo

2014-01-01

284

Profiling of serum metabolites in canine lymphoma using gas chromatography mass spectrometry.  

PubMed

Canine lymphoma is a common cancer that has high rates of complete remission with combination chemotherapy. However, the duration of remission varies based on multiple factors, and there is a need to develop a method for early detection of recurrence. In this study, we compared the metabolites profiles in serum from 21 dogs with lymphoma and 13 healthy dogs using gas chromatography mass spectrometry (GC-MS). The lymphoma group was separated from the control group in an orthogonal projection to latent structure with discriminant analysis (OPLS-DA) plot using ions of m/z 100-600, indicating that the metabolites profiles in lymphoma cases differed from those in healthy dogs. The lymphoma group was also separated from the control group on OPLS-DA plot using 29 metabolites identified in all serum samples. Significant differences were found for 16 of these metabolites with higher levels in the lymphoma group for 15 of the metabolites and lower levels for inositol. An OPLS-DA plot showed separation of the lymphoma and healthy groups using these 16 metabolites only. These results indicate that metabolites profile with GC-MS may be a useful tool for detection of potential biomarker and diagnosis of canine lymphoma. PMID:25131950

Tamai, Reo; Furuya, Masaru; Hatoya, Shingo; Akiyoshi, Hideo; Yamamoto, Ryohei; Komori, Yoshiaki; Yokoi, Shin-ichi; Tani, Kenichiro; Hirano, Yuji; Komori, Masayuki; Takenaka, Shigeo

2014-11-01

285

Evaluation of column hardware on liquid chromatography-mass spectrometry of phosphorylated compounds.  

PubMed

The influences of column hardware, such as chromatographic tubes and frits, on liquid chromatography-mass spectrometry (LC-MS) analysis of phosphorylated compounds were evaluated. The signal to noise ratio (S/N) and the intensity of flavin adenine dinucleotide (FAD) using a glass lined tube and polyethylene frit (GL-PE) column was approximately 170 and 90 times higher, respectively, than those using conventional stainless steel tube and stainless steel frit (S-S) column. In addition, the retention time of FAD using GL-PE column was the shortest compared to other columns. Interaction between phosphorylated compounds and metal ions in the flow path in the S-S column was stronger than that between them and the GL-PE column. Thus, the metal ions in the flow path in GL-PE column were low. Since the specific surface area of a pair of frits was 70 times larger than that of a chromatographic tube (150 mm×2.1 mm), the frits were found to have more effective improvement of the S/N as well as the intensity than the chromatographic tubes, when phosphorylated compounds were analyzed by LC-MS. When the evaluated phosphorylated compounds were analyzed by LC-MS(/MS) using a GL-PE column, the intensity and S/N were increased. PMID:25604270

Sakamaki, Hiroshi; Uchida, Takeharu; Lim, Lee Wah; Takeuchi, Toyohide

2015-02-13

286

Study on essential oils from four species of Zhishi with gas chromatography–mass spectrometry  

PubMed Central

Background Citrus fruits are widely used as food and or for medicinal purposes, and they contain a host of active substances that contribute to health. The immature fruits of Citrus sinensis Osbeck and its cultivars (CS), C. junos Sieb. ex Tanaka (CJ), C. aurantium L. and its cultivars (CA) and Poncirus trifoliate Raf. (PT) are the most commonly used medicinal herbs in Traditional Chinese Medicine, called Zhishi. And their mature fruits can be used as food. Results In this study, the essential oils of four different Zhishi species were extracted by steam distillation and detected using gas chromatography- mass spectrometry (GC-MS). A total of 39 volatiles from the four species were tentatively identified. The limonene was the most abundant amongst the four species. Principal component analysis (PCA) of essential oils showed a clear separation of volatiles among CS, CJ and PT. However, CA could not be separated from these three species. Additionally, the volatiles accounting for the variations among the widely separated species were characterized through their corresponding loading weight. Conclusion Sesquiterpenes were identified as characteristic markers for PT. The content of some monoterpenes could be as taxonomic markers between CS and CJ. This work is of great importance for the evaluation and authentication of Zhishi samples through essential oils. PMID:24708882

2014-01-01

287

Measurement of F2- isoprostanes and isofurans using gas chromatography-mass spectrometry.  

PubMed

F2-Isoprostanes (IsoPs) are isomers of prostaglandin F2? formed from the nonenzymatic free radical-catalyzed peroxidation of arachidonic acid. Since discovery of these molecules by Morrow and Roberts in 1990, F2-IsoPs have been shown to be excellent biomarkers as well as potent mediators of oxidative stress in vivo in humans. Isofurans (IsoFs) are also oxidation products generated from the nonenzymatic oxidation of arachidonic acid. IsoFs are preferentially formed instead of F2-IsoPs in settings of increased oxygen tension. The protocol presented herein is the current methodology that our laboratory uses to quantify F2-IsoPs and IsoFs in biological tissues and fluids using gas chromatography/mass spectrometry (GC/MS). A variety of analytical procedures to measure F2-IsoPs, including other GC/MS methods and liquid chromatography/MS and immunological approaches, are reported in the literature. This method provides a very low limit of quantitation and is suitable for analysis of both F2-IsoPs and IsoFs from a variety of biological sources including urine, plasma, tissues, cerebral spinal fluid, exhaled breath condensate, and amniotic fluid, among others. PMID:23044261

Milne, Ginger L; Gao, Benlian; Terry, Erin S; Zackert, William E; Sanchez, Stephanie C

2013-06-01

288

Open-access liquid chromatography/mass spectrometry in a drug discovery environment.  

PubMed

The use of open-access mass spectrometry to monitor synthetic chemistry reactions, and also the integrity and purity of new chemical entities, has been a part of the medicinal chemist's tool-box for more than 5 years. Originally in our group at Wyeth Research there were two open-access methods available to the chemists, flow injection analysis (FIA) and liquid chromatography/mass spectrometry (LC/MS). The FIA method was approximately 3 min long, while the LC/MS method was approximately 20 min long (including an 8 min gradient). Within the first 2 years, the total number of open-access analyses increased by approximately 125%. It is interesting, however, that the number of LC/MS analyses increased by more than 285%. This is attributed to the fact that the chemists began using the LC/MS data to monitor reactions and also to check final product integrity and purity. In addition, the number of chemists performing parallel synthesis reactions has increased; thus, individual chemists can produce sample sets of up to 100 vials. This paper describes the implementation of new methodology, which accommodates the need for much faster run times and also the ability to acquire alternating positive and negative ion spectra within the same run. In addition, the instrument has been configured to e-mail the resulting processed data report to the submitting chemist. Several methods have been developed, including structure elucidation using in-source collision-induced dissociation (CID) and night-time analysis. The LC/MS methods for this system are described herein and are applicable to both industrial and academic synthetic chemistry optimization efforts. PMID:12271431

Mallis, Larry M; Sarkahian, Ani B; Kulishoff, John M; Watts, William L

2002-09-01

289

Electro membrane extraction followed by low-density solvent based ultrasound-assisted emulsification microextraction combined with derivatization for determining chlorophenols and analysis by gas chromatography-mass spectrometry.  

PubMed

A highly efficient and simple two-step method, electro membrane extraction (EME) followed by low-density solvent based ultrasound-assisted emulsification microextraction (EME-LDS-USAEME) combined with derivatization and analysis by gas chromatography-mass spectrometry (GC-MS), was developed for the determination of trace level chlorophenols in environmental water samples. In the first step, the analytes were extracted, under electrical potential, from the sample solution into the acceptor solution, which was held in a polypropylene membrane sheet with 1-octanol as the supported liquid membrane. The acceptor solution from the first step was then employed as the sample solution for the second step of LDS-USAEME. In this step, the target analytes were extracted into a solvent with lower density than water that was dispersed in the sample solution with the assistance of ultrasound. The extract was separated from the sample solution by centrifugation and collected as the upper layer. Finally, the extract with a derivatization reagent were injected into a GC-MS system for analysis. Six chlorophenols, 2-chlorophenol, 4-chlorophenol, 2,3-dichlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol and pentachlorophenol were selected here as model compounds for developing and evaluating the method. Several factors influencing the extraction and derivatization were investigated. With the EME-LDS-USAEME procedure, high enrichment factors of up to 2198 were achieved. Under the most favorable conditions, good limits of detection (down to 0.005 ?g/L), linearity (from 0.05-10 to 0.2-10 ?g/L, depending on the analytes), and repeatability of extraction (RSDs below 9.7%, n=5) were obtained. The proposed method was applied to determine chlorophenols in drainwater samples. PMID:22579488

Guo, Liang; Lee, Hian Kee

2012-06-22

290

COMPUTER SURVEY OF GC/MS (GAS CHROMATOGRAPHY/MASS SPECTROMETRY) DATA ACQUIRED IN EPA'S (ENVIRONMENTAL PROTECTION AGENCY) PRIORITY POLLUTANT SCREENING ANALYSIS: SYSTEM AND RESULTS  

EPA Science Inventory

The screening analysis phase of the best available treatment (BAT) review of wastewater treatment techniques by EPA was initiated to assess 21 industrial categories for the 129 'priority pollutants.' Implicit in the purpose of the screening analysis for these pollutants was the n...

291

The role of the acquisition methods in the analysis of natural and synthetic steroids and cholic acids by gas chromatography–mass spectrometry  

Microsoft Academic Search

An exhaustive GC–MS acquisition study was performed, for the simultaneous analysis of natural and synthetic steroids and cholic acids (in order to insert them into the last tierce of our multiresidue analysis system), such as androsterone, ?-estradiol, transdehydroandro-sterone, transdehyroandrosterone, mestranol, dihydrotestosterone, ethinylestradiol, testosterone, norethisterone, estriol, 4-androstene-3,17-dione, gestodene, levonorgestrel, etonogestrel, coprostanol, progesterone, cholesterol, medroxyprogesterone-acetate, lithocholic acid, stigmasterol, cholic acid, chenodeoxycholic acid,

N. Andrási; A. Helenkár; A. Vasanits-Zsigrai; Gy. Záray; I. Molnár-Perl

2011-01-01

292

Headspace solid-phase microextraction gas chromatography-mass spectrometry and gas chromatography-olfactometry analysis of volatile compounds in pineapple breads.  

PubMed

Sensorial analysis of pineapple breads (conventionally baked, Cpb; fully baked frozen, Fpb and partially baked, Ppb) showed no significant differences in terms of aroma and taste. On the contrary, the scores for the overall quality between the partially baked and conventionally baked breads showed significant (p < 0.05) differences. At the same time, headspace analysis using a solid-phase microextraction (SPME) method identified 59 volatile compounds. The results of the aroma extracts dilution analysis (AEDA) revealed 19 most odour-active compounds with FD factors in the range of 32-128 as the key odourants of the pineapple breads. Further analysis of the similarities and differences between the pineapple breads in terms of the key odourants were carried out by the application of PLS-DA and PLS-regression coefficients. Results showed that Ppb exhibited strong positive correlations with most of the volatile- and non-volatile compounds, while the Cpb showed significant positive correlations with hexanal and 4-hydroxy-2,5-dimethyl-3(2H)-furanone, and the Fpb had strong positive correlations with lactic acid, benzoic acid, benzaldehyde and ethyl propanoate. PMID:23174897

Ying, Saw; Lasekan, Ola; Naidu, Kalla Reddi Mohan; Lasekan, Seye

2012-01-01

293

Method Development for the Analysis of 1,4-Dioxane in Drinking Water Using Solid Phase Extraction and Gas Chromatography/Mass Spectrometry  

EPA Science Inventory

1,4-Dioxane has been identified as a probable human carcinogen and an emerging contaminant in drinking water. The National Exposure Research Laboratory (NERL) has developed a method for the analysis of 1,4-dioxane in drinking water at ng/L concentrations. The method consists of...

294

Extract-filter-shoot liquid chromatography/mass spectrometry for analysis of vitamin D2 in a powdered supplement capsule and SRM 3280  

Technology Transfer Automated Retrieval System (TEKTRAN)

An ‘extract-filter-shoot’ method for analysis of vitamin D2, ergocalciferol, in a dry powdered dietary supplement capsule containing rice flour excipient and in National Institute of Standards and Technology (NIST) standard reference material (SRM) 3280 is reported. Quantification of vitamin D2 was...

295

On-line analysis of volatile chlorinated hydrocarbons in air by gas chromatography-mass spectrometry Improvements in preconcentration and injection steps.  

PubMed

An analytical system composed of a cryofocusing trap injector device coupled to a gas chromatograph with mass spectrometric detection (CTI-GC-MS) specific for the on-line analysis in air of volatile chlorinated hydrocarbons (VCHCs) (dichloromethane; chloroform; 1,1,1-trichloroethane; tetrachloromethane; 1,1,2-trichloroethylene; tetrachloroethylene) was developed. The cryofocusing trap injector was the result of appropriate low cost modifications to an original purge-and-trap device to make it suitable for direct air analysis even in the case of only slightly contaminated air samples, such as those from remote zones. The CTI device can rapidly and easily be rearranged into the purge-and-trap allowing water and air analysis with the same apparatus. Air samples, collected in stainless steel canisters, were introduced directly into the CTI-GC-MS system to realize cryo-concentration (at -120 degrees C), thermal desorption (at 200 degrees C) and for the subsequent analysis of volatiles. The operating phases and conditions were customised and optimized. Recovery efficiency was optimized in terms of moisture removal, cold trap temperature and sampling mass flow. The injection of entrapped volatiles was realized through a direct transfer with high chromatographic reliability (capillary column-capillary column). These improvements allowed obtaining limits of detection (LODs) at least one order of magnitude lower than current LODs for the investigated substances. The method was successfully employed on real samples: air from urban and rural areas and air from remote zones such as Antarctica. PMID:20444461

Zoccolillo, Lelio; Amendola, Luca; Insogna, Susanna; Pastorini, Elisabetta

2010-06-11

296

COMPARATIVE ANALYSIS OF POLYCHLORINATED DIBENZO-P-DIOXIN AND DIBENZOFURAN CONGENERS IN GREAT LAKES FISH EXTRACTS BY GAS CHROMATOGRAPHY-MASS SPECTROMETRY AND IN VITRO ENZYME INDUCTION ACTIVITIES  

EPA Science Inventory

The high-resolution gas chromatographic-mass spectrometric analysis of 25 Great Lakes fish extracts confirmed the identities of several 2,3,7,8-tetrasubstituted polychlorinated dibenzofurans (PCDFs) and dibenzo-p-dioxins (PCDDs). The dominant congener in extracts from Lake Michig...

297

Probing new approaches using atmospheric pressure photo ionization for the analysis of brominated flame retardants and their related degradation products by liquid chromatography–mass spectrometry  

Microsoft Academic Search

Atmospheric pressure photo ionisation has been evaluated for the analysis of brominated flame retardants and their related degradation products by LC–MS. Degradation mixtures obtained from the photochemical degradation of tetrabromobisphenol A and decabromodiphenylether were used as model systems for the assessment of the developed methodology. Negative ion mode gave best results for TBBPA and its degradation compounds. [M?H]? ions were

Laurent Debrauwer; Anne Riu; Majdouline Jouahri; Estelle Rathahao; Isabelle Jouanin; Jean-Philippe Antignac; Ronan Cariou; Bruno Le Bizec; Daniel Zalko

2005-01-01

298

Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory - Determination of Moderate-Use Pesticides and Selected Degradates in Water by C-18 Solid-Phase Extraction and Gas Chromatography/Mass Spectrometry  

USGS Publications Warehouse

A method for the isolation and analysis of 21 parent pesticides and 20 pesticide degradates in natural-water samples is described. Water samples are filtered to remove suspended particulate matter and then are pumped through disposable solid-phase-extraction columns that contain octadecyl-bonded porous silica to extract the analytes. The columns are dried by using nitrogen gas, and adsorbed analytes are eluted with ethyl acetate. Extracted analytes are determined by capillary-column gas chromatography/mass spectrometry with selected-ion monitoring of three characteristic ions. The upper concentration limit is 2 micrograms per liter (?g/L) for most analytes. Single-operator method detection limits in reagent-water samples range from 0.00 1 to 0.057 ?g/L. Validation data also are presented for 14 parent pesticides and 20 degradates that were determined to have greater bias or variability, or shorter holding times than the other compounds. The estimated maximum holding time for analytes in pesticide-grade water before extraction was 4 days. The estimated maximum holding time for analytes after extraction on the dry 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. The method complements existing U.S. Geological Survey Method O-1126-95 (NWQL Schedules 2001 and 2010) by using identical sample preparation and comparable instrument analytical conditions so that sample extracts can be analyzed by either method to expand the range of analytes determined from one water sample.

Sandstrom, Mark W.; Stroppel, Max E.; Foreman, William T.; Schroeder, Michael P.

2001-01-01

299

Methods of Analysis by the U.S. Geological Survey Organic Geochemistry Research Group-Update and Additions to the Determination of Chloroacetanilide Herbicide Degradation Compounds in Water Using High-Performance Liquid Chromatography/Mass Spectrometry  

USGS Publications Warehouse

An analytical method using high-performance liquid chromatography/mass spectrometry (HPLC/MS) was developed by the U.S. Geological Survey in 1999 for the analysis of selected chloroacetanilide herbicide degradation compounds in water. These compounds were acetochlor ethane sulfonic acid (ESA), acetochlor oxanilic acid (OXA), alachlor ESA, alachlor OXA, metolachlor ESA, and metolachlor OXA. The HPLC/MS method was updated in 2000, and the method detection limits were modified accordingly. Four other degradation compounds also were added to the list of compounds that can be analyzed using HPLC/MS; these compounds were dimethenamid ESA, dimethenamid OXA, flufenacet ESA, and flufenacet OXA. Except for flufenacet OXA, good precision and accuracy were demonstrated for the updated HPLC/MS method in buffered reagent water, surface water, and ground water. The mean HPLC/MS recoveries of the degradation compounds from water samples spiked at 0.20 and 1.0 ?g/L (microgram per liter) ranged from 75 to 114 percent, with relative standard deviations of 15.8 percent or less for all compounds except flufenacet OXA, which had relative standard deviations ranging from 11.3 to 48.9 percent. Method detection levels (MDL's) using the updated HPLC/MS method varied from 0.009 to 0.045 ?g/L, with the flufenacet OXA MDL at 0.072 ?g/L. The updated HPLC/MS method is valuable for acquiring information about the fate and transport of the parent chloroacetanilide herbicides in water.

Lee, E.A.; Kish, J.L.; Zimmerman, L.R.; Thurman, E.

2001-01-01

300

Analysis of post-translational modifications in recombinant monoclonal antibody IgG1 by reversed-phase liquid chromatography/mass spectrometry.  

PubMed

Characterization and quantitative analysis of modifications in recombinant monoclonal antibodies (mAbs) plays an important role in biopharmaceutical development. This study demonstrates a new approach to assess variants in mAbs, based on individual analysis of subdomains. These subdomains were generated by dithiothreitol reduction and papain cleavage. A reversed-phase LC-MS method was developed that provides efficient separation of subdomains (light and heavy chains, Fab and Fc) containing several specific modifications such as pyroglutamic acid, deamidation, isomerization and oxidation. The best separation was achieved on Zorbax SB C8 columns using linear water-acetonitrile gradients in 0.1% trifluoroacetic acid. Deconvoluted electrospray ionization mass spectra of these domains revealed the modification profiles of these variants with high accuracy and resolution. This study presents a strategy that offers orthogonal approaches to analyze antibody variants, and provide a qualitative and quantitative assessment of mAb heterogeneity. PMID:17640657

Yan, Boxu; Valliere-Douglass, John; Brady, Lowell; Steen, Sean; Han, Mei; Pace, Danielle; Elliott, Susan; Yates, Zac; Han, Yihong; Balland, Alain; Wang, Weichun; Pettit, Dean

2007-09-14

301

Analysis of eight capsaicinoids in peppers and pepper-containing foods by high-performance liquid chromatography and liquid chromatography-mass spectrometry.  

PubMed

Diverse procedures have been reported for the isolation and analysis of secondary metabolites called capsaicinoids, pungent compounds in the fruit of the Capsicum (Solanaceae) plant. To further improve the usefulness of high-performance liquid chromatography (HPLC), studies were carried out on the analysis of extracts containing up to eight of the following capsaicinoids: capsaicin, dihydrocapsaicin, homocapsaicin-I, homocapsaicin-II, homodihydrocapsaicin-I, homodihydrocapsaicin-II, nonivamide, and nordihydrocapsaicin. HPLC was optimized by defining effects on retention times of (a) the composition of the mobile phase (acetonitrile/0.5% formic acid in H2O), (b) the length of the Inertsil column, and (c) the capacity values (k) of the column packing. Identification was based on retention times and mass spectra of individual peaks. Quantification was based on the UV response at 280 nm in HPLC and recoveries from spiked samples. The method (limit of detection of approximately 15-30 ng) was successfully used to quantify capsaicinoid levels of parts of the pepper fruit (pericarp, placenta, seeds, and in the top, middle, and base parts of whole peppers) in 17 species of peppers and in 23 pepper-containing foods. The results demonstrate the usefulness of the method for the analysis of capsaicinoids ranging from approximately 0.5 to 3600 microg of capsaicin equiv/g of product. The water content of 12 fresh peppers ranged from 80.8 to 92.7%. The described freeze-drying, extraction, and analysis methods should be useful for assessing the distribution of capsaicinoids in the foods and in defining the roles of these biologically active compounds in the plant, the diet, and medicine. PMID:16277419

Kozukue, Nobuyuki; Han, Jae-Sook; Kozukue, Etsuko; Lee, Sin-Jung; Kim, Joung-Ae; Lee, Kap-Rang; Levin, Carol E; Friedman, Mendel

2005-11-16

302

Foodomics platform for the assay of thiols in wines with fluorescence derivatization and ultra performance liquid chromatography mass spectrometry using multivariate statistical analysis.  

PubMed

The presence of specific volatile and aminothiols in wine is associated with quality, worth, price, and taste. The identification of specific thiol-containing compounds in various wines has been reported in many valuable and interesting works. In this study, a novel foodomics assay of thiol-containing compounds, such as free aminothiols and related conjugates, was developed using ultra performance liquid chromatography (UPLC) with fluorescence (FL) and electrospray (ESI) time-of-flight mass spectrometric (TOF/MS) detections. FL specific derivatization was applied along with multivariate statistical analysis. First, the optimal experimental conditions were studied using representative thiols, such as l-cysteine, N-acetyl-l-cysteine, cysteamine, and l-glutathione, and then the UPLC-FL derivatization and separation steps were fixed for the subsequent screening of unknown thiol-containing compounds. The screening assay consisted of monitoring the UPLC-TOF/MS peaks of unknown thiols, which decreased due to the derivatization as compared to the nonderivatized thiols. The principal component analysis of the UPLC-TOF/MS data could be well-differentiated and categorized into two groups. The orthogonal signal correction partial least-squares discriminant analysis, the so-called S-plot, showed that the quality differentiation is directly related to the decrease of native thiols and increase of derivatized thiols. With this strategy, the mass difference from the derivatization reagent (+m/z 198) could be utilized for the identification of these thiols using the FL peaks retention time and metabolomics-databases. The presence of l-glutathione in rice wine was for the first time reported on the basis of the available metabolomics-databases and standard matching. This novel concept based on foodomics could be applied in food analysis for the ready screening of specific functional compounds by exploiting the various derivatization modes available. PMID:23339461

Inoue, Koichi; Nishimura, Maiko; Tsutsui, Haruhito; Min, Jun Zhe; Todoroki, Kenichiro; Kauffmann, Jean-Michel; Toyo'oka, Toshimasa

2013-02-13

303

Extraction of pesticides, dioxin-like PCBs and PAHs in water based commodities using liquid–liquid microextraction and analysis by gas chromatography–mass spectrometry  

Microsoft Academic Search

Water based samples such as flavored drinks, juices and drinking water may contain contaminants at ultra trace level belonging to different chemical classes. A novel, simple, low-cost and fast method was developed and validated for trace residue extraction of pesticides, dioxin-like PCBs and PAHs from water and water based samples followed by analysis through gas chromatography (GC) coupled with time-of-flight

Soma Dasgupta; Kaushik Banerjee; Sagar Utture; Parijat Kusari; Sameer Wagh; Kondiba Dhumal; Sanjay Kolekar; Pandurang G. Adsule

2011-01-01

304

Analysis of French and American oak chips with different toasting degrees by headspace solid-phase microextraction-gas chromatography-mass spectrometry.  

PubMed

This paper describes the optimisation of headspace solid-phase microextraction (HS-SPME) conditions for the analysis of volatile compounds in oak chips used to accelerate wine aging as an alternative to traditional aging in oak barrels. The direct extraction of ground wood samples and the extraction of sample aqueous slurries using a divinylbenzene-carboxen-polydimethylsiloxane (DVB-CAR-PDMS) fibre were studied and compared. Optimal conditions for direct extraction were 110 degrees C and 60 min, whereas for aqueous slurries they were obtained by adding 2mL of a 7.1 molL(-1) sodium chloride solution, at 70 degrees C and for 60 min. The two optimised HS-SPME approaches were compared in terms of repeatability and extraction efficiency; water addition to the sample prior to HS-SPME was selected because it yielded better repeatability (6.6% versus 8.5% relative standard deviation) and efficiency (around 1.4-4.8 times higher analyte amount extracted for most of the compounds). Finally, the method was applied in the analysis of oak chip samples from American and French oak with different degrees of toasting. Principal component analysis (PCA) of the results showed that the first principal component was correlated with the toasting degree whereas the second, which was strongly influenced by whisky lactones and eugenol, allowed us to differentiate between American and French oak chips. PMID:17964587

Bozalongo, Ruth; Carrillo, José David; Torroba, Miguel Angel Fernández; Tena, María Teresa

2007-11-30

305

Analysis of non-esterified fatty acids in human samples by solid-phase-extraction and gas chromatography/mass spectrometry.  

PubMed

The determination of the fatty acid (FA) profile of lipid classes is essential for lipidomic analysis. We recently developed a GC/MS-method for the analysis of the FA profile of total FAs, i.e. the totality of bound and unbound FAs, in any given biological sample (TOFAs). Here, we present a method for the analysis of non-esterified fatty acids (NEFAs) in biological samples, i.e. the fraction that is present as extractable free fatty acids. Lipid extraction is performed according to Dole using 80/20 2-propanol/n-hexane (v/v), with 0.1% H2SO4. The fatty acid-species composition of this NEFA-fraction is determined as FAME after derivatization with our GC/MS-method on a BPX column (Shimadzu). Validation of the NEFA-method presented was performed in human plasma samples. The validated method has been used with human plasma, cells and tissues, as well as mammalian body fluids and tissue samples. The newly developed solid-phase-extraction (SPE)-GC-MS method allows the rapid separation of the NEFA-fraction from a neutral lipid extract of plasma samples. As a major advantage compared to G-FID-methods, GC-MS allows the use of stable isotope labeled fatty acid precursors to monitor fatty acid metabolism. PMID:24036177

Kopf, Thomas; Schmitz, Gerd

2013-11-01

306

Development of a sensitive and selective liquid chromatography-mass spectrometry method for high throughput analysis of paralytic shellfish toxins using graphitised carbon solid phase extraction.  

PubMed

Routine regulatory monitoring of paralytic shellfish toxins (PST) commonly employs oxidative derivitisation and complex liquid chromatography fluorescence detection methods (LC-FL). The pre-column oxidation LC-FL method is currently implemented in New Zealand and the United Kingdom. When using this method positive samples are fractionated and two different oxidations are required to confirm the identity and quantity of each PST analogue present. There is a need for alternative methods that are simpler, provide faster turnaround times and have improved detection limits. Hydrophilic interaction liquid chromatography (HILIC) HPLC-MS/MS analysis of PST has been used for research purposes, but high detection limits and substantial sample matrix issues have prevented it from becoming a viable alternative for routine monitoring purposes. We have developed a HILIC UPLC-MS/MS method for paralytic shellfish toxins with an optimised desalting clean-up procedure on inexpensive carbon solid phase extraction cartridges for reduction of matrix interferences. This represents a major technical breakthrough and allows sensitive, selective and rapid analysis of paralytic shellfish toxins from a variety of sample types, including many commercially produced bivalve molluscan shellfish species. Additionally, this analytical approach avoids the need for complex calculations to determine sample toxicity, as unlike other methods each PST analogue is able to be quantified as a single resolved peak. This article presents the method development and optimisation information. A thorough single laboratory validation study has subsequently been performed and this data will be presented elsewhere. PMID:25704772

Boundy, Michael J; Selwood, Andrew I; Harwood, D Tim; McNabb, Paul S; Turner, Andrew D

2015-03-27

307

Multiresidue analysis of plant growth regulators in grapes by triple quadrupole and quadrupole-time of flight-based liquid chromatography/mass spectrometry.  

PubMed

A selective and sensitive LC-MS/MS method is presented for simultaneous determination of 12 plant growth regulators, viz., indol-3-acetic acid, indol-3-butyric acid, kinetin, zeatin, 6-benzyl aminopurine, gibberellic acid, abscisic acid, chlormequat chloride, forchlorfenuron, paclobutrazole, daminozide, and 2,4-dichlorophenoxy acetic acid, in bud sprouts and grape berries. The sample preparation method involved extraction of homogenized sample (5 g) with 40 mL methanol (80%), and final determination was by LC-MS/MS in the multiple reaction monitoring (MRM) mode with time segmentation for quantification supported by complementary analysis by quadrupole-time of flight (Q-TOF) MS with targeted high-resolution MS/MS scanning for confirmatory identification based on accurate mass measurements. The recovery of the test compounds ranged within 90-107% with precision RSD less than 5% (n = 6). The method could be successfully applied in analyzing incurred residue samples, and the strength of accurate mass analysis could be utilized in identifying the compounds in cases where the qualifier MRM ions were absent or at an S/N less than 3:1 due to low concentrations. PMID:22320078

Oulkar, Dasharath P; Banerjee, Kaushik; Kulkarni, Sunil

2011-01-01

308

Polymer-coated sample cup for quantitative analysis of semi-volatile phthalates in polymeric materials by thermal desorption-gas chromatography-mass spectrometry.  

PubMed

A new "polymer-coated" sample cup useful for the analysis of phthalates in polymeric materials by thermal desorption (TD)-GC/MS using a temperature programmable furnace type pyrolyzer as a TD device was developed to suppress the emission of semi-volatile phthalates such as dimethyl phthalate (DMP) and diethyl phthalate (DEP) during the measurements. The inner surface of a sample cup was coated by polymers which act as a sorbent for the phthalates. Three polymers, polyvinyl chloride, polystyrene and poly (methyl methacrylate), were chosen as the coating polymers. A mixture of ten phthalates including DMP and DEP was used as the test sample to estimate the performance of the sample cups. When a conventional sample cup without any polymer coating was used, 90 and 50% reductions in the peak areas of DMP and DEP were respectively observed at the waiting time of 200min. On the contrary, no reduction of peak area of DMP and DEP during the same waiting time was observed with any one of the three coating polymers at the proper polymer film thickness. These results suggest that the polymer-coated sample cup suppresses the emission of semi-volatile phthalates and is effective for the analysis of phthalates containing DMP and DEP by TD-GC/MS. PMID:25795398

Hosaka, Akihiko; Watanabe, Atsushi; Watanabe, Chuichi; Teramae, Norio; Ohtani, Hajime

2015-04-24

309

Automated dispersive liquid-liquid microextraction-gas chromatography-mass spectrometry.  

PubMed

An innovative automated procedure, low-density solvent based/solvent demulsification dispersive liquid-liquid microextraction (automated DLLME) coupled to gas chromatography-mass spectrometry (GC/MS) analysis, has been developed. The most significant innovation of the method is the automation. The entire procedure, including the extraction of the model analytes (phthalate esters) by DLLME from the aqueous sample solution, breaking up of the emulsion after extraction, collection of the extract, and analysis of the extract by GC/MS, was completely automated. The applications of low-density solvent as extraction solvent and the solvent demulsification technique to break up the emulsion simplified the procedure and facilitated its automation. Orthogonal array design (OAD) as an efficient optimization strategy was employed to optimize the extraction parameters, with all the experiments conducted auotmatically. An OA16 (4(1) × 2(12)) matrix was initially employed for the identification of optimized extraction parameters (type and volume of extraction solvent, type and volume of dispersive solvent and demulsification solvent, demulsification time, and injection speed). Then, on the basis of the results, more levels (values) of five extraction parameters were investigated by an OA16 (4(5)) matrix and quantitatively assessed by the analysis of variance (ANOVA). Enrichment factors of between 178- and 272-fold were obtained for the phthalate esters. The linearities were in the range of 0.1 and 50 ?g/L and 0.2 and 50 ?g/L, depending on the analytes. Good limits of detection (in the range of 0.01 to 0.02 ?g/L) and satisfactory repeatability (relative standard deviations of below 5.9%) were obtained. The proposed method demonstrates for the first time integrated sample preparation by DLLME and analysis by GC/MS that can be operated automatically across multiple experiments. PMID:24666227

Guo, Liang; Lee, Hian Kee

2014-04-15

310

Preparation of phenyl group-functionalized magnetic mesoporous silica microspheres for fast extraction and analysis of acetaldehyde in mainstream cigarette smoke by gas chromatography-mass spectrometry.  

PubMed

Acetaldehyde is regarded as a toxic mainstream cigarette smoke constituent, and measurement of acetaldehyde in complex real samples is difficult owing to its high volatility and reactivity. In this work, phenyl group-functionalized magnetic mesoporous microspheres were developed as the solid-phase extraction sorbents for enrichment and analysis of acetaldehyde in mainstream cigarette smoke. The functional magnetic microspheres were first synthesized through a facile one-pot co-condensation approach. The prepared nanomaterials possessed abundant silanol groups in the exterior surface and numerous phenyl groups in the interior pore-walls, as well as a large surface area (273.5m(2)/g), strong superparamagnetism and uniform mesopores (3.3 nm). Acetaldehyde in mainstream cigarette smoke was collected in water and derivatizated with O-2,3,4,5,6-(pentafluorobenzyl)hydroxylamine. The formed acetaldehyde oximes were extracted and enriched by the prepared adsorbents via ?-? interactions and subsequently analyzed using GC-MS. Extraction conditions such as amounts of sorbents, eluting solvent, adsorption and desorption time were investigated and optimized to achieve the best efficiency. Method validations including linearity, recovery, repeatability, and limit of detection were also studied. It was found that the suggested methodology provided low detection limit of 0.04 mg/mL, good recovery of 88-92%, intra-day and inter-day RSD values of 4.5% and 10.1%, and linear range of 0.25-4 mg/mL (R(2)=0.999). The results indicated that the proposed method based on phenyl-functionalized magnetic mesoporous microspheres was rapid, efficient and convenient for the enrichment and analysis of acetaldehyde in tobacco. PMID:24054614

Huang, Danni; Sha, Yunfei; Zheng, Saijing; Liu, Baizhan; Deng, Chunhui

2013-10-15

311

Study on the photostability of guaiazulene by high-performance liquid chromatography/mass spectrometry and gas chromatography/mass spectrometry.  

PubMed

The photostability of guaiazulene (1,4-dimethyl-7-isopropylazulene; GA), a natural azulenic compound used in cosmetic and health-care products, as well as in pharmaceutical preparations, was investigated in solution (methanol, ethanol, acetonitrile), by different techniques: gas chromatography/mass spectrometry (GC/MS) and high-performance liquid chromatography combined with atmospheric pressure chemical ionization mass spectrometry and UV detection (LC/APCI-MS and HPLC/UV). A solar simulator (xenon-arc lamp) was used as UV-A radiation source. The study involved: monitoring compound decomposition, identifying products of photodegradation (PPs), assessing the role of oxygen and evaluating the kinetics of the process. Minor PPs are volatile compounds and were characterized by GC/MS, while oligomeric polyoxygenated compounds, tentatively characterized on the basis of MS and MS/MS spectra, were found to be the main photoproducts. The photodegradation was found to be enhanced by the presence of oxygen; nevertheless, determination of the singlet oxygen quantum yield for GA gave a lower value than that for the reference standard Rose Bengal. The obtained results and the developed stability-indicating methods (GC/MS and LC/MS) are of interest for stability studies and/or quality control purposes of GA as raw material or cosmetic products. PMID:18680092

Fiori, Jessica; Gotti, Roberto; Albini, Angelo; Cavrini, Vanni

2008-09-01

312

The role of the acquisition methods in the analysis of natural and synthetic steroids and cholic acids by gas chromatography-mass spectrometry.  

PubMed

An exhaustive GC-MS acquisition study was performed, for the simultaneous analysis of natural and synthetic steroids and cholic acids (in order to insert them into the last tierce of our multiresidue analysis system), such as androsterone, ?-estradiol, transdehydroandro-sterone, transdehyroandrosterone, mestranol, dihydrotestosterone, ethinylestradiol, testosterone, norethisterone, estriol, 4-androstene-3,17-dione, gestodene, levonorgestrel, etonogestrel, coprostanol, progesterone, cholesterol, medroxyprogesterone-acetate, lithocholic acid, stigmasterol, cholic acid, chenodeoxycholic acid, ?-sitosterol, ursodeoxycholic acid, 3-hydroxy-7-ketocholic acid and dehydrocholic acid, in total 26 compounds. As novelties to the field, for the trimethylsilyl (TMS) oxime ether/ester derivatives of steroids and cholic acids, at first, a tandem mass spectrometric (MS/MS), multiple reaction monitoring (MRM) type acquisition method has been developed in a single run; also for the first time, the three acquisition techniques, the full scan (FS), the selective ion monitoring (SIM), in our case the multiple ion monitoring (MIM) and the currently optimized MRM methods, have been compared; all three, in parallel, under strictly the same derivatization/instrumental conditions, both in matrix free solutions and municipal wastewater from two Hungarian wastewater treatment plants (WWTPs). Critical evaluation of the three acquisition protocols was collated on their analytical performances and validated under the same conditions. The data of six point calibration curves for FS, MIM and MRM methods, showed that both R² (0.9995, 0.9858, 0.9975) and RSD (5.3, 5.8, 5.0), for two parallel derivatizations, each injected three times, proved to be independent of the acquisition processes. Whereas, for the method limit of quantification (LOQ) and the instrument limit of quantification (ILQ) values showed considerable differences. LOQ data, were decreasing in the FS, MIM, MRM line (expressed in ng/L), for all steroids and cholic acids. The same trend was determined in terms of the ILQ values. The practical utility of the optimized acquisition techniques was confirmed by the quantitation of the steroids and cholic acids contents of wastewater samples. Results confirmed the importance of the MRM acquisition method, even in comparison to the MIM one: with particular interest in selected cases: avoiding the extreme overestimation of the ?-estradiol (156-1325%) and that of the ethinylestradiol (582-831%) concentrations in the wastewater samples. PMID:21981935

Andrási, N; Helenkár, A; Vasanits-Zsigrai, A; Záray, Gy; Molnár-Perl, I

2011-11-11

313

Identification of volatile compounds in poultry manure by gas chromatography-mass spectrometry.  

PubMed

Volatile components in poultry manure were isolated by freeze vacuum distillation and continuous extraction, and 72 compounds were identified by gas chromatography and gas chromatography-mass spectrometry. Branched alipathic alcohols, many esters, dimethyl trisulphide and alkanamides were detected for the first time. Carboxylic acids, sulphides, alkanamides, phenols and indoles were formed during rotting. Judging from the ratio of concentration to the threshold value (detectable amount of odour) of each component detected in poultry manure, the most important odorous components were butyric acid, 3-methylbutyric acid, dimethyl trisulphide, indole and skatole. PMID:3558630

Yashuhara, A

1987-01-30

314

Analysis of volatile phenols in alcoholic beverage by ethylene glycol-polydimethylsiloxane based stir bar sorptive extraction and gas chromatography-mass spectrometry.  

PubMed

An ethylene glycol (EG)/polydimethylsiloxane (PDMS) copolymer based stir bar sorptive extraction (SBSE)-GC-MS method was developed for the analysis of volatile phenols (4-ethylphenol, 4-vinylphenol, 4-ethylguaiacol, and 4-vinylguaiacol) in alcoholic beverages. The beverage samples were diluted with phosphate buffer (1M, pH 7) and extracted with an EG/PDMS stir bar. Volatile phenols were thermally desorbed and analyzed by GC-MS. Parameters affecting extraction efficiency were studied including ionic strength, pH, extraction time, ethanol content and nonvolatile matrix. Good correlation coefficients with R(2) in the range of 0.994-0.999 were obtained for volatile phenol concentration of 5-500?g/L. Recovery for all phenols were from 95.7% to 104.4% in a beer matrix and 81.4% to 97.6% in a wine matrix. The method had a standard deviation less than 5.8% for all volatile phenols. The limit of quantification (LOQs) in beer samples was lower than 3?g/L. The method was further applied to analyze the concentrations of volatile phenols in beer, wine and other alcoholic beverage samples. PMID:25766496

Zhou, Qin; Qian, Yanping; Qian, Michael C

2015-04-17

315

Simultaneous determination of glucose turnover, alanine turnover, and gluconeogenesis in human using a double stable-isotope-labeled tracer infusion and gas chromatography-mass spectrometry analysis  

SciTech Connect

We have developed and validated a new method to measure simultaneously glucose turnover, alanine turnover, and gluconeogenesis in human, in steady and non-steady states, using a double stable-isotope-labeled tracer infusion and GC-MS analysis. The method is based on the concomitant infusion and dilution of D-(2,3,4,6,6-2H5)glucose and L-(1,2,3-13C3)alanine. The choice of the tracers was done on the basis of a minimal overlap between the ions of interest and those arising from natural isotopic abundances. Alanine was chosen as the gluconeogenic substrate because it is the major gluconeogenic amino acid extracted by the liver and, with lactate, constitutes the bulk of the gluconeogenic precursors. The method was validated by comparing the results obtained during simultaneous infusion of trace amounts of both stable isotope labeled compounds with the radioactive tracers (D-(3-3H)glucose and L-(1,2,3-14C3)alanine) in a normal and a diabetic subject; the radiolabeled tracers were used as the accepted reference procedure. A slight overestimation of glucose turnover (7.3 versus 6.8 in normal and 10.8 versus 9.2 mumol/kg min in diabetic subject) was noticed when the stable isotope-labeled tracers were used. For the basal turnover rate of alanine, similar values were obtained with both methods (6.2 mumol/kg min). For gluconeogenesis, higher values were observed in the basal state with the stable isotopes (0.42 versus 0.21 mumol/kg min); however, these differences disappeared in the postprandial period after the ingestion of a mixed meal. Despite those minor differences, the overall correlation with the reference method was excellent for glucose turnover (r = 0.87) and gluconeogenesis (r = 0.86).

Martineau, A.; Lecavalier, L.; Falardeau, P.; Chiasson, J.L.

1985-12-01

316

Extraction of pure components from overlapped signals in gas chromatography-mass spectrometry (GC-MS)  

PubMed Central

Gas chromatography-mass spectrometry (GC-MS) is a widely used analytical technique for the identification and quantification of trace chemicals in complex mixtures. When complex samples are analyzed by GC-MS it is common to observe co-elution of two or more components, resulting in an overlap of signal peaks observed in the total ion chromatogram. In such situations manual signal analysis is often the most reliable means for the extraction of pure component signals; however, a systematic manual analysis over a number of samples is both tedious and prone to error. In the past 30 years a number of computational approaches were proposed to assist in the process of the extraction of pure signals from co-eluting GC-MS components. This includes empirical methods, comparison with library spectra, eigenvalue analysis, regression and others. However, to date no approach has been recognized as best, nor accepted as standard. This situation hampers general GC-MS capabilities, and in particular has implications for the development of robust, high-throughput GC-MS analytical protocols required in metabolic profiling and biomarker discovery. Here we first discuss the nature of GC-MS data, and then review some of the approaches proposed for the extraction of pure signals from co-eluting components. We summarize and classify different approaches to this problem, and examine why so many approaches proposed in the past have failed to live up to their full promise. Finally, we give some thoughts on the future developments in this field, and suggest that the progress in general computing capabilities attained in the past two decades has opened new horizons for tackling this important problem. PMID:19818154

Liki?, Vladimir A

2009-01-01

317

Triple sorbent thermal desorption/gas chromatography/mass spectrometry determination of vapor phase organic contaminants  

SciTech Connect

A thermal desorption/ps chromatography/mass spectrometry (TD/GC/MS) has been evaluated for the determination of volatile organic compounds (VOCS) in vapor phase samples using Carbosieve S-III/Carbotrap/Carotrap C triple sorbent traps (TST) similar to those available from a commercial source. The analysis was carried out with a Hewlett-Packard 5985A or 5995 GC/MS system with a modified injector to adapt an inhouse manufactured short-path desorber for transferring desorbate directly onto a cryofocusing loop for subsequent GC/MS analysis. Vapor phase standards generated from twenty six compounds were used for method validation, including alkanes, alkyl alcohols, alkyl ketones, and alkyl nitrites, a group of representative compounds that have previously been identified in a target airborne matrix. The method was validated based on the satisfactory results in terms of reproducibility, recovery rate, stability, and linearity. A relative, standard deviation of 0.55 to 24.3 % was obtained for the entire TD process (generation of gas phase standards, spiking the standards on and desorbing from TST) over a concentration range of 20 to 500 ng/trap. Linear correlation coefficients for the calibration curves as determined ranged from 0.81 to 0.99 and limits of detection ranged from 3 to 76 ng. For a majority of standards, recoveries of greater than 90% were observed. For three selected standards spiked on TSTS, minimal loss (10 to 22%) was observed after storing the spiked in, a 4{degree}C refrigerator for 29 days. The only chromatographable artifact observed was a 5% conversion of isopropanol to acetone. The validated method been successfully applied, to the determination of VOCs collected from various emission sources in a diversified concentration range.

Ma, C.Y.; Skeen, J.T.; Dindal, A.B.; Higgins, C.E.; Jenkins, R.A.

1994-05-01

318

Methods of analysis by the U. S. Geological Survey National Water Quality Laboratory; determination of pesticides in water by graphitized carbon-based solid-phase extraction and high-performance liquid chromatography/mass spectrometry  

USGS Publications Warehouse

In 1996, the U.S. Geological Survey National Water Quality Laboratory (NWQL) developed and implemented a graphitized carbon-based solid-phase extraction and high-performance liquid chromatographic analytical method to determine polar pesticide concentrations in surface- and ground-water samples. Subsequently, the NWQL developed a complementary analysis that uses high-performance liquid chromatography/mass spectrometry to detect, identify, and quantify polar pesticides and pesticide metabolites in filtered water at concentrations as low as 10 nanograms per liter. This new method was designed to improve sensitivity and selectivity over the prior method, and to reduce known interferences from natural organic matter. In this new method, pesticides are extracted from filtered water samples by useing a 0.5-gram graphitized carbon-based solid-phase extraction cartridge, eluted from the cartridge, and concentrations determined by using high-perforance liquid chromatography with elecrospray ionization-mass spectrometry. The upper concentratoin limit is 1.000 microgram per liter (ug/L) for most compounds. Single-operator method detection limits in organic-free water samples fortified with pesticdes at a concentration of 0.025 ug/L ranged from 0.0019 to 0.022 ug/L for all compunds in the method. The grand mean (mean of mean recoveries for individual compounds) recoveries in organic-free water samples ranged from 72 to 89 percent, fortified wit hpesticides at three concentrations between 0.025 and 0.5 ug/L. Grand mean recoveries in ground- and surface-water samples ranged from 46 to 119 percent, also fortified with pesticies at three concentrations between 0.025 and 0.5 ug/L. Long-term recoveries from reagent water spikes were used to demonstrate that 38 of 65 compounds can be reported without qualification of the quantitative result across the analytical range of the method. The remaining 27 are reported with qualified estimates of concentration because of greater variability of recovery.

Furlong, Edward T.; Anderson, Bruce D.; Werner, Stephen L.; Soliven, Paul P.; Coffey, Laura J.; Burkhardt, Mark R.

2001-01-01

319

Ultra-performance liquid chromatography-mass spectrometry as a sensitive and powerful technology in lipidomic applications.  

PubMed

Lipidomics, the comprehensive illumination of lipid-based information in biology systems, involves in identifying lipids and profiling lipids and lipid-derived mediators. The development of lipidomics enables the characterization of lipid species and detailed lipid profiling in body fluid, tissue or cell, and allows for a wider understanding of the biological roles of lipid networks. Lipidomic research has been greatly facilitated by recent advances in ultra-performance liquid chromatography-mass spectrometry (UPLC-MS) and involved in lipid extraction, lipid identification and data analysis supporting applications from qualitative and quantitative assessment of multiple lipid species. UPLC technique, different mass spectrometry technique, lipid extraction and data analysis in lipidomics are reviewed. Afterwards, examples are provided on the use of UPLC-MS for finding lipid biomarkers in disease, drug, food, nutrition and plant fields. We also discuss the UPLC-MS-based lipidomics for the future perspectives and their potential problems. PMID:25014415

Zhao, Ying-Yong; Wu, Shao-Ping; Liu, Shuman; Zhang, Yongmin; Lin, Rui-Chao

2014-09-01

320

[Determination of residual glycol ethers in leather and leather products by gas chromatography/mass spectrometry].  

PubMed

An effective method was established for the simultaneous determination of residual glycol ethers in leather and leather products by gas chromatography/mass spectrometry. Glycol ethers in leather and leather products were ultrasonically extracted at 45 °C, using ethyl acetate as the extraction solvent. The extracts were purified by solid phase extraction (SPE) columns, and then analyzed by gas chromatography/mass spectrometry in selected ion monitoring mode. The content of each analyte was calibrated by external standard method. The limit of detection of ethylene glycol ethyl ether (EGEE) was 0. 10 mg/kg under the condition of signal to noise (S/N) of 3 and the limits of the other 11 glycol ethers were all less than 0.05 mg/kg. The spiked recoveries varied from 81. 2% to 95. 5% at three different spiked levels with the relative standard deviations (RSDs) ranged from 1.4% to 6. 6%. The proposed method is simple, rapid and accurate, with the limits of detection much less than the requirements of the Regulation Concerning Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) of European Union. It is applicable to the determination of residual glycol ethers in leather and leather products, and provides a reference for the relevant testing standards. PMID:25507726

Wang, Ghengyun; Zhang, Weiya; Li, Lixia; Shen, Yalei; Lin, Junfeng; Xie, Tangtang; Chu, Naiqing

2014-08-01

321

[Determination of residual glycol ethers in leather and leather products by gas chromatography/mass spectrometry].  

PubMed

An effective method was established for the simultaneous determination of residual glycol ethers in leather and leather products by gas chromatography/mass spectrometry. Glycol ethers in leather and leather products were ultrasonically extracted at 45 °C, using ethyl acetate as the extraction solvent. The extracts were purified by solid phase extraction (SPE) columns, and then analyzed by gas chromatography/mass spectrometry in selected ion monitoring mode. The content of each analyte was calibrated by external standard method. The limit of detection of ethylene glycol ethyl ether (EGEE) was 0. 10 mg/kg under the condition of signal to noise (S/N) of 3 and the limits of the other 11 glycol ethers were all less than 0.05 mg/kg. The spiked recoveries varied from 81. 2% to 95. 5% at three different spiked levels with the relative standard deviations (RSDs) ranged from 1.4% to 6. 6%. The proposed method is simple, rapid and accurate, with the limits of detection much less than the requirements of the Regulation Concerning Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) of European Union. It is applicable to the determination of residual glycol ethers in leather and leather products, and provides a reference for the relevant testing standards. PMID:25434128

Wang, Ghengyun; Zhang, Weiya; Li, Lixia; Shen, Yalei; Lin, Junfeng; Xie, Tangtang; Chu, Naiqing

2014-08-01

322

Simultaneous determination of dimethylamphetamine and its metabolites in rat hair by gas chromatography-mass spectrometry.  

PubMed

In order to study the disposition of dimethylamphetamine (DMAP) and its metabolites, DMAP N-oxide, methamphetamine (MA) and amphetamine (AP), from plasma to hair in rats, a simultaneous determination method for these compounds in biological samples using gas chromatography-mass spectrometry with selected ion monitoring (GC-MS-SIM) was developed. As DMAP N-oxide partially degrades to DMAP and MA during GC-MS analysis, it was necessary to avoid conditions which co-extract the N-oxide in the sample preparation so as to assure no contribution of artifactual products from DMAP N-oxide in the detection of the other compounds. For confirmation of the satisfactory separation of DMAP N-oxide from the others, the internal standards used for quantification were labeled with different numbers of deuterium atoms. Determination of unchanged DMAP was performed without any derivatization, that of DMAP N-oxide was carried out after conversion into trifluoroacetyl-MA by reaction with trifluoroacetic anhydride, and MA and AP were quantified after trifluoroacetyl-derivatization. After intraperitoneal administration of DMAP HCI to pigmented hairy rats (5 mgkg(-1) day(-1), 10 days, n=3), concentrations of DMAP and its metabolites in urine, plasma and hair were measured by GC-MS-SIM. The area under the concentration versus time curves (AUCs) of DMAP, DMAP N-oxide, MA and AP in the plasma were 397.2+/-97.5, 279.7+/-68.3, 18.4+/-1.2 and 15.9+/-2.2 microg min ml(-1), while their concentrations in the hair newly grown for 4 weeks after administration were 4.82+/-0.67. 0.45+/-0.09, 3.25+/-0.36 and 0.89+/-0.05 ng mg(-1), respectively. This fact suggested that the incorporation tendency of DMAP N-oxide from plasma into hair was distinctly low in comparison with the other compounds. PMID:10872586

Kikura, R; Nakahara, Y; Kojima, S

2000-05-12

323

Serum metabolic profiling of human gastric cancer based on gas chromatography/mass spectrometry  

PubMed Central

Research on molecular mechanisms of carcinogenesis plays an important role in diagnosing and treating gastric cancer. Metabolic profiling may offer the opportunity to understand the molecular mechanism of carcinogenesis and help to non-invasively identify the potential biomarkers for the early diagnosis of human gastric cancer. The aims of this study were to explore the underlying metabolic mechanisms of gastric cancer and to identify biomarkers associated with morbidity. Gas chromatography/mass spectrometry (GC/MS) was used to analyze the serum metabolites of 30 Chinese gastric cancer patients and 30 healthy controls. Diagnostic models for gastric cancer were constructed using orthogonal partial least squares discriminant analysis (OPLS-DA). Acquired metabolomic data were analyzed by the nonparametric Wilcoxon test to find serum metabolic biomarkers for gastric cancer. The OPLS-DA model showed adequate discrimination between cancer and non-cancer cohorts while the model failed to discriminate different pathological stages (I-IV) of gastric cancer patients. A total of 44 endogenous metabolites such as amino acids, organic acids, carbohydrates, fatty acids, and steroids were detected, of which 18 differential metabolites were identified with significant differences. A total of 13 variables were obtained for their greatest contribution in the discriminating OPLS-DA model [variable importance in the projection (VIP) value >1.0], among which 11 metabolites were identified using both VIP values (VIP >1) and the Wilcoxon test. These metabolites potentially revealed perturbations of glycolysis and of amino acid, fatty acid, cholesterol, and nucleotide metabolism of gastric cancer patients. These results suggest that gastric cancer serum metabolic profiling has great potential in detecting this disease and helping to understand its metabolic mechanisms. PMID:22124703

Song, Hu; Peng, Jun-Sheng; Yao, Dong-Sheng; Yang, Zu-Li; Liu, Huan-Liang; Zeng, Yi-Ke; Shi, Xian-Ping; Lu, Bi-Yan

2011-01-01

324

Relative binding affinities of integrin antagonists by equilibrium dialysis and liquid chromatography-mass spectrometry.  

PubMed

The integrin ?v?6 is a potential target for treatment of idiopathic pulmonary fibrosis (IPF). Equilibrium dialysis (ED) was investigated for its ability to report ligand binding in an ?v?6 inhibitor screening assay. As a preliminary experiment, an established peptidomimetic inhibitor of the integrin was dialyzed against ?v?6, and the fraction bound (f b) and percentage saturation determined by liquid chromatography-mass spectrometry (LC-MS) analysis. Quantitation of the inhibitor in the two chambers of the ED cartridge revealed an uneven distribution in the presence of ?v?6, corresponding to near saturation binding to the protein (93 ± 3%), while the control (without integrin) showed an equal partitioning of the inhibitor on either side of the dialysis membrane. A competitive ED assay with a 12 component mixture of antagonists was conducted, and the results compared with an established cell adhesion assay for quantifying ?v?6 inhibition of individual antagonists. Compounds clustered into three groupings: those with pIC 50 values between ca. 5.0 and 5.5, which possessed ED f b values indistinguishable from the controls, those with pIC 50s of 6.5 ± 0.2, which exhibited detectable integrin binding (f b 13-25%) in the ED assay, and a single compound of pIC 50 7.2 possessing an f b value of 38%. A good correlation between ED-derived f b and pIC 50 was observed despite the two assays utilizing quite different outputs. These results demonstrate that ED with LC-MS detection shows promise as a rapid ?v?6 integrin antagonist screening assay for mixtures of putative ligands. PMID:25699153

Tipping, William J; Tshuma, Nkazimulo; Adams, James; Haywood, Harvey T; Rowedder, James E; Fray, M Jonathan; McInally, Thomas; Macdonald, Simon J F; Oldham, Neil J

2015-02-12

325

Automated mass correction and data interpretation for protein open-access liquid chromatography-mass spectrometry.  

PubMed

Characterization of recombinant protein purification fractions and final products by liquid chromatography-mass spectrometry (LC/MS) are requested more frequently each year. A protein open-access (OA) LC/MS system was developed in our laboratory to meet this demand. This paper compares the system that we originally implemented in our facilities in 2003 to the one now in use, and discusses, in more detail, recent enhancements that have improved its robustness, reliability, and data reporting capabilities. The system utilizes instruments equipped with reversed-phase chromatography and an orthogonal accelerated time-of-flight mass spectrometer fitted with an electrospray source. Sample analysis requests are accomplished using a simple form on a web-enabled laboratory information management system (LIMS). This distributed form is accessible from any intranet-connected company desktop computer. Automated data acquisition and processing are performed using a combination of in-house (OA-Self Service, OA-Monitor, and OA-Analysis Engine) and vendor-supplied programs (AutoLynx, and OpenLynx) located on acquisition computers and off-line processing workstations. Analysis results are then reported via the same web-based LIMS. Also presented are solutions to problems not addressed on commercially available, small-molecule OA-LC/MS systems. These include automated transforming of mass-to-charge (m/z) spectra to mass spectra and automated data interpretation that considers minor variants to the protein sequence-such as common post-translational modifications (PTMs). Currently, our protein OA-LC/MS platform runs on five LC/MS instruments located in three separate GlaxoSmithKline R&D sites in the US and UK. To date, more than 8000 protein OA-LC/MS samples have been analyzed. With these user friendly and highly automated OA systems in place, mass spectrometry plays a key role in assessing the quality of recombinant proteins, either produced at our facilities or bought from external sources, without dedicating extensive amounts of analyst resource. PMID:17221927

Wagner, Craig D; Hall, John T; White, Wendy L; Miller, Luke A D; Williams, Jon D

2007-02-01

326

Investigation of the temperature stability of premarin intravenous using liquid chromatography-mass spectrometry.  

PubMed

Stability of Premarin(®)Intravenous was investigated in dry and reconstituted forms by monitoring major components in samples for a period of six months, using liquid chromatography-mass spectrometry. The components, largely comprising a series of estrogen and steroid hormone sulfates, were considered to be fairly stable (variation?10%) for dry samples stored at room temperature and at 38°C (100°F) during the experimental time frame. However, significant variation, especially after 2 months of storage, was observed in reconstituted solutions. This variation was significantly larger for samples stored at elevated vs. room temperature. It was interesting to note that the concentration of equilenin sulfate increased over time, whereas that of other major components were seen to fluctuate and decrease. This phenomenon was partially explained by the conversion of equilin compounds into their corresponding equilenin forms, a phenomenon which was further investigated through a storage study with pure standard solutions and by tandem mass spectrometry. PMID:21444176

Nguyen, Hien P; Tedmon, Lauren; Li, Li; Wigginton, Jane G; Maass, David; Gatson, Joshua W; Simpkins, James W; Schug, Kevin A

2011-07-15

327

Analysis of organo-chlorine pesticides residue in raw coffee with a modified "quick easy cheap effective rugged and safe" extraction/clean up procedure for reducing the impact of caffeine on the gas chromatography-mass spectrometry measurement.  

PubMed

The control of pesticide residues on raw coffee is a task of great importance due to high consumption of this beverage in Italy and in many other countries. High caffeine content can hamper extraction and measurement of any pesticide residue. A tandem extraction protocol has been devised by exploiting the quick easy cheap effective rugged and safe (QuEChERS) scheme for extraction, coupled to a dispersive liquid-liquid micro-extraction (DLLME) in order to drastically reduce caffeine content in the final extract. Gas chromatography-mass spectrometry (GC-MS) has been used for quantification of organo-chlorine pesticides in single ion monitoring (SIM) mode. Method has been validated and performances meet the criteria prescribed by European Union regulations. PMID:25537171

Bresin, Bruno; Piol, Maria; Fabbro, Denis; Mancini, Maria Antonietta; Casetta, Bruno; Del Bianco, Clorinda

2015-01-01

328

Analysis of acrylonitrile, 1,3-butadiene, and related compounds in acrylonitrile-butadiene-styrene copolymers for kitchen utensils and children's toys by headspace gas chromatography/mass spectrometry.  

PubMed

A headspace gas chromatography/mass spectrometry method was developed for the simultaneous determination of the residual levels of acrylonitrile (AN), 1,3-butadiene (1,3-BD), and their related compounds containing propionitrile (PN) and 4-vinyl-1-cyclohexene (4-VC) in acrylonitrile-butadiene-styrene (ABS) copolymers for kitchen utensils and children's toys. A sample was cut into small pieces, then N,N-dimethylacetamide and an internal standard were added in a sealed headspace vial. The vial was incubated for 1 h at 90 degrees C and the headspace gas was analyzed by gas chromatography/mass spectrometry. The recovery rates of the analytes were 93.3-101.8% and the coefficients of variation were 0.3-6.5%. In ABS copolymers, the levels were 0.3-50.4 microg/g for AN, ND-4.5 microg/g for PN, 0.06-1.58 microg/g for 1,3-BD, and 1.1-295 microg/g for 4-VC. The highest level was found for 4-VC, which is a dimer of 1,3-BD, and the next highest was for AN, which is one of the monomers of the ABS copolymer. Furthermore, the method was also applied to acrylonitrile-styrene (AS) copolymers and polystyrenes (PS) for kitchen utensils, and nitrile-butadiene rubber (NBR) gloves. In AS copolymers, AN and PN were detected at 16.8-54.5 and 0.8-6.9 microg/g, respectively. On the other hand, the levels in PS and NBR samples were all low. PMID:21313827

Ohno, Hiroyuki; Kawamura, Yoko

2010-01-01

329

Identification of Unknown Contaminants in Water Samples from ISS Employing Liquid Chromatography/Mass Spectrometry/Mass Spectrometry  

NASA Technical Reports Server (NTRS)

Mass Spectrometry/Mass Spectrometry (MS/MS) is a powerful technique for identifying unknown organic compounds. For non-volatile or thermally unstable unknowns dissolved in liquids, liquid chromatography/mass spectrometry/mass spectrometry (LC/MS/MS) is often the variety of MS/MS used for the identification. One type of LC/MS/MS that is rapidly becoming popular is time-of-flight (TOF) mass spectrometry. This technique is now in use at the Johnson Space Center for identification of unknown nonvolatile organics in water samples from the space program. An example of the successful identification of one unknown is reviewed in detail in this paper. The advantages of time-of-flight instrumentation are demonstrated through this example as well as the strategy employed in using time-of-flight data to identify unknowns.

Rutz, Jeffrey A.; Schultz, John R.

2008-01-01

330

[Advances of metabolite identification in liquid chromatography-mass spectrometry based metabolomics].  

PubMed

Liquid chromatography-mass spectrometry (LC-MS) based metabolomics has become an important approach in life science research due to its powerful separation and high sensitivity detection. However, because of the lack of an effective mass spectra library for metabolite identification, a vast amount of detected metabolites are unable to be identified. The improvement of the metabolite coverage and the discovery of biomarkers are harmed, leading to the severe loss of chemical and biological information. The metabolite identification has become a major bottleneck in metabolomics studies. This review describes recent advances of metabolite identification based on atmospheric pressure ionization (API)-MS data. In particular, it focuses on the advances in mass spectrometer instruments, assignment of elemental compositions, database and spectral search, computer-aided spectral interpretation, etc. PMID:25739265

Kong, Hongwei; Dai, Weidong; Xu, Guowang

2014-10-01

331

Principles and Applications of Liquid Chromatography-Mass Spectrometry in Clinical Biochemistry  

PubMed Central

Liquid chromatography-mass spectrometry (LC-MS) is now a routine technique with the development of electrospray ionisation (ESI) providing a simple and robust interface. It can be applied to a wide range of biological molecules and the use of tandem MS and stable isotope internal standards allows highly sensitive and accurate assays to be developed although some method optimisation is required to minimise ion suppression effects. Fast scanning speeds allow a high degree of multiplexing and many compounds can be measured in a single analytical run. With the development of more affordable and reliable instruments, LC-MS is starting to play an important role in several areas of clinical biochemistry and compete with conventional liquid chromatography and other techniques such as immunoassay. PMID:19224008

Pitt, James J

2009-01-01

332

Metabolic effect of an exogenous gene on transgenic Beauveria bassiana using liquid chromatography-mass spectrometry-based metabolomics.  

PubMed

Genetic modification of Beauveria bassiana with the scorpion neurotoxin aaIT gene can distinctly increase its insecticidal activity, whereas the effect of this exogenous gene on the metabolism of B. bassiana is unknown until now. Thus, we investigate the global metabolic profiling of mycelia and conidia of transgenic and wild-type B. bassiana by liquid chromatography-mass spectrometry (LC-MS). Principal component analysis (PCA) and orthogonal projection to latent structure discriminant analysis (OPLS-DA) reveal clear discrimination of wild-type mycelia and conidia from transgenic mycelia and conidia. The decrease of glycerophospholipids, carnitine, and fatty acids and the increase of oxylipins, glyoxylate, pyruvic acid, acetylcarnitine, fumarate, ergothioneine, and trehalose in transgenic mycelia indicate the enhanced oxidative reactions. In contrast, most metabolites related to oxidative stress are not altered significantly in conidia, which implies that there will be no significant oxidative stress reaction when the aaIT gene is quiescent in cells. PMID:23822565

Luo, Feifei; Lu, Ruili; Zhou, Hong; Hu, Fenglin; Bao, Guanhu; Huang, Bo; Li, Zengzhi

2013-07-17

333

Authentication of organically and conventionally grown basils by gas chromatography/mass spectrometry chemical profiles.  

PubMed

Basil plants cultivated by organic and conventional farming practices were accurately classified by pattern recognition of gas chromatography/mass spectrometry (GC/MS) data. A novel extraction procedure was devised to extract characteristic compounds from ground basil powders. Two in-house fuzzy classifiers, i.e., the fuzzy rule-building expert system (FuRES) and the fuzzy optimal associative memory (FOAM) for the first time, were used to build classification models. Two crisp classifiers, i.e., soft independent modeling by class analogy (SIMCA) and the partial least-squares discriminant analysis (PLS-DA), were used as control methods. Prior to data processing, baseline correction and retention time alignment were performed. Classifiers were built with the two-way data sets, the total ion chromatogram representation of data sets, and the total mass spectrum representation of data sets, separately. Bootstrapped Latin partition (BLP) was used as an unbiased evaluation of the classifiers. By using two-way data sets, average classification rates with FuRES, FOAM, SIMCA, and PLS-DA were 100 ± 0%, 94.4 ± 0.4%, 93.3 ± 0.4%, and 100 ± 0%, respectively, for 100 independent evaluations. The established classifiers were used to classify a new validation set collected 2.5 months later with no parametric changes except that the training set and validation set were individually mean-centered. For the new two-way validation set, classification rates with FuRES, FOAM, SIMCA, and PLS-DA were 100%, 93%, 97%, and 100%, respectively. Thereby, the GC/MS analysis was demonstrated as a viable approach for organic basil authentication. It is the first time that a FOAM has been applied to classification. A novel baseline correction method was used also for the first time. The FuRES and the FOAM are demonstrated as powerful tools for modeling and classifying GC/MS data of complex samples, and the data pretreatments are demonstrated to be useful to improve the performance of classifiers. PMID:23398171

Wang, Zhengfang; Chen, Pei; Yu, Liangli; Harrington, Peter de B

2013-03-01

334

Authentication of Organically and Conventionally Grown Basils by Gas Chromatography/Mass Spectrometry Chemical Profiles  

PubMed Central

Basil plants cultivated by organic and conventional farming practices were accurately classified by pattern recognition of gas chromatography/mass spectrometry (GC/MS) data. A novel extraction procedure was devised to extract characteristic compounds from ground basil powders. Two in-house fuzzy classifiers, i.e., the fuzzy rule-building expert system (FuRES) and the fuzzy optimal associative memory (FOAM) for the first time, were used to build classification models. Two crisp classifiers, i.e., soft independent modeling by class analogy (SIMCA) and the partial least-squares discriminant analysis (PLS-DA), were used as control methods. Prior to data processing, baseline correction and retention time alignment were performed. Classifiers were built with the two-way data sets, the total ion chromatogram representation of data sets, and the total mass spectrum representation of data sets, separately. Bootstrapped Latin partition (BLP) was used as an unbiased evaluation of the classifiers. By using two-way data sets, average classification rates with FuRES, FOAM, SIMCA, and PLS-DA were 100 ± 0%, 94.4 ± 0.4%, 93.3 ± 0.4%, and 100 ± 0%, respectively, for 100 independent evaluations. The established classifiers were used to classify a new validation set collected 2.5 months later with no parametric changes except that the training set and validation set were individually mean-centered. For the new two-way validation set, classification rates with FuRES, FOAM, SIMCA, and PLS-DA were 100%, 83%, 97%, and 100%, respectively. Thereby, the GC/MS analysis was demonstrated as a viable approach for organic basil authentication. It is the first time that a FOAM has been applied to classification. A novel baseline correction method was used also for the first time. The FuRES and the FOAM are demonstrated as powerful tools for modeling and classifying GC/MS data of complex samples and the data pretreatments are demonstrated to be useful to improve the performance of classifiers. PMID:23398171

Wang, Zhengfang; Chen, Pei; Yu, Liangli; Harrington, Peter de B.

2013-01-01

335

Performance Evaluation of three Liquid Chromatography Mass Spectrometry Methods for Broad Spectrum Drug Screening  

PubMed Central

BACKGROUND Liquid chromatography-mass spectrometry (LC-MS) and tandem LC-MS (LC-MS/MS) are increasingly used in toxicology laboratories as a complementary method to gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-ultraviolet detection (LC-UV) for comprehensive drug screening (CDS). This study was designed to characterize the sensitivity and specificity of three LC-MS(/MS) vendor-supplied methods for targeted CDS and identify the current limitations associated with the use of these technologies. METHODS Five methods for broad spectrum CDS, including LC-UV (REMEDi), full scan GC-MS, LC-MS (ZQ™-Mass Detector with MassLynx™-software), LC-QTRAP-MS/MS (3200-QTRAP® with Cliquid®-software) and LC-LIT-MS/MS (LXQ™ Linear Ion Trap with ToxID™-software) were evaluated based on their ability to detect drugs in 48 patient urine samples. RESULTS The tandem MS methods identified 15% more drugs than the single stage MS or LC-UV methods. Use of two broad spectrum screening methods identified more drugs than any single system alone. False negatives and false positives generated by the LC-MS(/MS) software programs were identified upon manual review of the raw data. CONCLUSIONS The LC-MS/MS methods detected a broader menu of drugs; however, it is essential to establish manual data review criteria for all LC-MS(/MS) drug screening methods. Use of an EI-GC-MS and ESI-LC-MS/MS combination for targeted CDS may be optimal due to the complementary nature of the chromatographic and ionization techniques. PMID:20540936

Lynch, Kara L.; Breaud, Autumn R.; Vandenberghe, Hilde; Wu, Alan H. B.; Clarke, William

2010-01-01

336

A gas chromatography-mass spectrometry-based metabolomic approach for the characterization of goat milk compared with cow milk.  

PubMed

In this work, the polar metabolite pool of commercial caprine milk was studied by gas chromatography-mass spectrometry and multivariate statistical data analysis. Experimental data were compared with those of cow milk and the discriminant analysis correctly classified milk. By the same means, differences due to heat treatments (UHT or pasteurization) on milk samples were also investigated. Results of the 2 discriminant analyses were combined, with the aim of finding the discriminant metabolites unique for each class and shared by 2 classes. Valine and glycine were specific to goat milk, talose and malic acid to cow milk, and hydroxyglutaric acid to pasteurized samples. Glucose and fructose were shared by cow milk and UHT-treated samples, whereas ribose was shared by pasteurized and goat milk. Other discriminant variables were not attributed to specific metabolites. Furthermore, with the aim to reduce food fraud, the issue of adulteration of caprine milk by addition of cheaper bovine milk has been also addressed. To this goal, mixtures of goat and cow milk were prepared by adding the latter in a range from 0 to 100% (vol/vol) and studied by multivariate regression analysis. The error in the level of cow milk detectable was approximately 5%. These overall results demonstrated that, through the combined approach of gas chromatography-mass spectrometry and multivariate statistical data analysis, we were able to discriminate between milk typologies on the basis of their polar metabolite profiles and to propose a new analytical method to easily discover food fraud and to protect goat milk uniqueness. The use of appropriate visualization tools improved the interpretation of multivariate model results. PMID:25108860

Scano, Paola; Murgia, Antonio; Pirisi, Filippo M; Caboni, Pierluigi

2014-10-01

337

Plasma metabolomic profiling of dairy cows affected with ketosis using gas chromatography/mass spectrometry  

PubMed Central

Background Ketosis is an important problem for dairy cows` production performance. However, it is still little known about plasma metabolomics details of dairy ketosis. Results A gas chromatography/mass spectrometry (GC/MS) technique was used to investigate plasma metabolic differences in cows that had clinical ketosis (CK, n=22), subclinical ketosis (SK, n=32), or were clinically normal controls (NC, n=22). The endogenous plasma metabolome was measured by chemical derivatization followed by GC/MS, which led to the detection of 267 variables. A two-sample t-test of 30, 32, and 13 metabolites showed statistically significant differences between SK and NC, CK and NC, and CK and SK, respectively. Orthogonal signal correction-partial least-square discriminant analysis (OPLS-DA) revealed that the metabolic patterns of both CK and SK were mostly similar, with the exception of a few differences. The development of CK and SK involved disturbances in many metabolic pathways, mainly including fatty acid metabolism, amino acid metabolism, glycolysis, gluconeogenesis, and the pentose phosphate pathway. A diagnostic model arbitrary two groups was constructed using OPLS-DA and receiver–operator characteristic curves (ROC). Multivariate statistical diagnostics yielded the 19 potential biomarkers for SK and NC, 31 for CK and NC, and 8 for CK and SK with area under the curve (AUC) values. Our results showed the potential biomarkers from CK, SK, and NC, including carbohydrates, fatty acids, amino acids, even sitosterol and vitamin E isomers, etc. 2-piperidinecarboxylic acid and cis-9-hexadecenoic acid were closely associated with metabolic perturbations in ketosis as Glc, BHBA and NEFA for dealing with metabolic disturbances of ketosis in clinical practice. However, further research is needed to explain changes of 2,3,4-trihydroxybutyric acid, 3,4-dihydroxybutyric acid, ?-aminobutyric acid, methylmalonic acid, sitosterol and ?-tocopherol in CK and SK, and to reveal differences between CK and SK. Conclusion Our study shows that some new biomarkers of ketosis from plasma may find new metabolic changes to have clinically new utility and significance in diagnosis, prognosis, and prevention of ketosis in the future. PMID:24070026

2013-01-01

338

Determination of O-ethyl S-2-diisopropylaminoethyl methylphosphonothioate (VX) by thermospray liquid chromatography-mass spectrometry.  

PubMed

The determination of the nerve agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothioate (VX) by thermospray liquid chromatography-mass spectrometry was studied. The solvent system acetonitrile-methanol-0.25 M ammonium acetate was used on a reversed-phase C18 column. By selected ion monitoring at the protonated molecular ion of VX (m/z 268), the predominant peak in its thermospray mass spectrum, an amount of 200 pg could be detected. For the determination of VX in water at levels below 1 ng/ml, preconcentration by C18 cartridges was investigated. The applicability of the method was demonstrated by the determination of VX in spiked river waters. A concentration of 0.1 ng/ml could be detected starting from a water sample of 50 ml. A second application concerned the analysis of water extracts of spiked soil samples. PMID:2090658

Wils, E R; Hulst, A G

1990-12-01

339

Rapid determination of quetiapine in blood by gas chromatography-mass spectrometry. Application to post-mortem cases.  

PubMed

A simple, fast and sensitive method for the determination of quetiapine in human blood has been developed and validated. The method involved a basic liquid-liquid extraction procedure and subsequent analysis by gas chromatography-mass spectrometry, previous derivatization with bis(trimethylsilyl)-trifluoro-acetamide and chorotrimethylsilane (99 : 1). The methods of validation included linearity with a correlation coefficient?>?0.99 over the range 0.02-1?µg?ml(-1), intra- and interday precision (always?

López-Guarnido, Olga; Tabernero, María Jesús; Hernández, Antonio F; Rodrigo, Lourdes; Bermejo, Ana M

2014-10-01

340

Pyrolysis-gas chromatography/mass spectrometry analyses of biological particulates collected during recent space shuttle missions  

NASA Technical Reports Server (NTRS)

Biological particulates collected on air filters during shuttle missions (STS-40 and STS-42) were identified using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). A method was developed for identifying the atmospheric particles and their sources through the analysis of standard materials and the selection of "marker" compounds specific to the particle type. Pyrolysis spectra of biological standards were compared with those of airborne particles collected during two space shuttle missions; marker compounds present in the shuttle particle spectra were matched with those of the standards to identify the source of particles. Particles of 0,5--1-mm diameter and weighing as little as 40 micrograms could be identified using this technique. The Py-GC/MS method identified rat food and soilless plant-growth media as two sources of particles collected from the shuttle atmosphere during flight.

Matney, M. L.; Limero, T. F.; James, J. T.

1994-01-01

341

Pharmacokinetic Studies of Chinese Medicinal Herbs Using an Automated Blood Sampling System and Liquid Chromatography-mass Spectrometry.  

PubMed

The safety of herbal products is one of the major concerns for the modernization of traditional Chinese medicine, and pharmacokinetic data of medicinal herbs guide us to design the rational use of the herbal formula. This article reviews the advantages of the automated blood sampling (ABS) systems for pharmacokinetic studies. In addition, three commonly used sample preparative methods, protein precipitation, liquid-liquid extraction and solid-phase extraction, are introduced. Furthermore, the definition, causes and evaluation of matrix effects in liquid chromatography-mass spectrometry (LC/MS) analysis are demonstrated. Finally, we present our previous works as practical examples of the application of ABS systems and LC/MS for the pharmacokinetic studies of Chinese medicinal herbs. PMID:24716112

Wu, Yu-Tse; Wu, Ming-Tsang; Lin, Chia-Chun; Chien, Chao-Feng; Tsai, Tung-Hu

2012-01-01

342

Headspace solid-phase microextraction for characterization of fragrances of lemon verbena (Aloysia triphylla) by gas chromatography-mass spectrometry.  

PubMed

Natural fragrances from lemon verbena (Aloysia triphylla) were studied by headspace solid phase microextraction (HS-SPME) techniques followed by gas chromatography-mass spectrometry (GC-MS), with six different fibre coatings being tested to evaluate the extraction efficiencies of several selected compounds. A total of 14 compounds were identified in the fragrances of lemon verbena. Geranial and neral were detected as major components and alpha-pinene, beta-pinene, beta-caryophyllene, and curcumene as minor components. Enantiomeric analysis of chiral compounds from lemon verbena was carried out on a chiral column. alpha-Pinene, limonene, and camphor in the fragrances emitted from lemon verbena were found in the (+), (-), and (-) forms, respectively. PMID:15335064

Kim, Nam-Sun; Lee, Dong-Sun

2004-01-01

343

Ink dating using thermal desorption and gas chromatography/mass spectrometry: comparison of results obtained in two laboratories.  

PubMed

An ink dating method based on solvent analysis was recently developed using thermal desorption followed by gas chromatography/mass spectrometry (GC/MS) and is currently implemented in several forensic laboratories. The main aims of this work were to implement this method in a new laboratory to evaluate whether results were comparable at three levels: (i) validation criteria, (ii) aging curves, and (iii) results interpretation. While the results were indeed comparable in terms of validation, the method proved to be very sensitive to maintenances. Moreover, the aging curves were influenced by ink composition, as well as storage conditions (particularly when the samples were not stored in "normal" room conditions). Finally, as current interpretation models showed limitations, an alternative model based on slope calculation was proposed. However, in the future, a probabilistic approach may represent a better solution to deal with ink sample inhomogeneity. PMID:25389038

Koenig, Agnès; Bügler, Jürgen; Kirsch, Dieter; Köhler, Fritz; Weyermann, Céline

2015-01-01

344

MEASUREMENT OF POLYCYCLIC AROMATIC HYDROCARBONS IN SOILS AND SEDIMENTS BY PARTICLE-BEAM/HIGH-PERFORMANCE/LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY  

EPA Science Inventory

An analytical method was developed for the measurement of certain polycyclic aromatic hydrocarbons (PANs) in soils and sediments by particle beam liquid chromatography/mass spectrometry. he method applies to PANs with a molecular weight greater than 220. Samples are prepared by S...

345

Use of gas chromatography–mass spectrometry combined with resolution methods to characterize the essential oil components of Iranian cumin and caraway  

Microsoft Academic Search

Gas chromatography–mass spectrometry combined with iterative and non-iterative resolution methods was used to characterize the essential oil components of Iranian cumin and caraway. Orthogonal projection resolution (OPR) as a non-iterative and distance-selection-multivariate curve resolution-alternative least squares (DS-MCR-ALS) as an iterative method were used as auxiliary means to the analysis in the case of overlapping peaks. A total of 19 and

Mehdi Jalali-Heravi; Behrooz Zekavat; Hassan Sereshti

2007-01-01

346

Determination of acetone in human breath by gas chromatography–mass spectrometry and solid-phase microextraction with on-fiber derivatization  

Microsoft Academic Search

Analysis of breath acetone has been used as a diagnostic tool for diabetes. Due to its nature of volatility and activity, it is very difficult to accurately measure the concentration of acetone in human breath by gas chromatography–mass spectrometry (GC–MS). To overcome this problem, we developed a new method using GC–MS and solid-phase microextraction (SPME) with on-fiber derivatization to determine

Chunhui Deng; Jie Zhang; Xiaofeng Yu; Wei Zhang; Xiangmin Zhang

2004-01-01

347

Gas chromatography\\/mass spectrometry identification of long-term excreted metabolites of the anabolic steroid 4-chloro-1,2-dehydro-17?-methyltestosterone in humans  

Microsoft Academic Search

The misuse of anabolic steroids by athletes has been banned by sports organizations and is controlled by the analysis of urine samples obtained from athletes using gas chromatography\\/mass spectrometry (GC\\/MS). To extend the retrospectivity of the analytical methods, research is focused on long-term excreted metabolites. Preliminary results concerning the long-term detection of metabolites of the anabolic androgenic steroid 4-chloro-1,2-dehydro-17?-methyltestosterone I

W. Schänzer; S. Horning; G. Opfermann; M. Donike

1996-01-01

348

Determination of Alkylphenol Ethoxylates and Their Acetic Acid Derivatives in Drinking Water by Particle Beam Liquid Chromatography\\/Mass Spectrometry  

Microsoft Academic Search

Particle beam liquid chromatography\\/mass spectrometry (PB\\/LC\\/MS) was used to analyze finished drinking water for non-volatile organic compounds. 500 liters of finished water were extracted with an on-line continuous liquid\\/liquid extractor with dichloromethane at pH 7.4. PB\\/LC\\/MS was an excellent tool to detect and identify ng\\/L concentrations of alkylphenol polyethoxylates (n = 3?8), materials which went undetected by on-column gas chromatography\\/mass

Linda B. Clark; Robert T. Rosen; Thomas G. Hartman; Judith B. Louis; I. H. Suffet; R. L. Lippincott; Joseph D. Rosen

1992-01-01

349

Method of analysis and quality-assurance practices by the U.S. Geological Survey Organic Geochemistry Research Group; determination of geosmin and methylisoborneol in water using solid-phase microextraction and gas chromatography/mass spectrometry  

USGS Publications Warehouse

A method for the determination of two common odor-causing compounds in water, geosmin and 2-methylisoborneol, was modified and verified by the U.S. Geological Survey's Organic Geochemistry Research Group in Lawrence, Kansas. The optimized method involves the extraction of odor-causing compounds from filtered water samples using a divinylbenzene-carboxen-polydimethylsiloxane cross-link coated solid-phase microextraction (SPME) fiber. Detection of the compounds is accomplished using capillary-column gas chromatography/mass spectrometry (GC/MS). Precision and accuracy were demonstrated using reagent-water, surface-water, and ground-water samples. The mean accuracies as percentages of the true compound concentrations from water samples spiked at 10 and 35 nanograms per liter ranged from 60 to 123 percent for geosmin and from 90 to 96 percent for 2-methylisoborneol. Method detection limits were 1.9 nanograms per liter for geosmin and 2.0 nanograms per liter for 2-methylisoborneol in 45-milliliter samples. Typically, concentrations of 30 and 10 nanograms per liter of geosmin and 2-methylisoborneol, respectively, can be detected by the general public. The calibration range for the method is equivalent to concentrations from 5 to 100 nanograms per liter without dilution. The method is valuable for acquiring information about the production and fate of these odor-causing compounds in water.

Zimmerman, L.R.; Ziegler, A.C.; Thurman, E.M.

2002-01-01

350

Liquid chromatography-mass spectrometry with ionspray and electrospray interfaces in pharmaceutical and biomedical research.  

PubMed

Electrospray and ionspray techniques use samples that exist as ions or ion-molecule complexes in solution. After the dispersion of the solution into an electrically charged aerosol, the sample ions may escape from the solution into the gas phase in a region that is at atmospheric pressure. The sample ions are transported into the mass analyser which is operated under a high vacuum. Liquid chromatographs can be coupled to electrospray and ionspray interfaces. Flow injection or continuous infusion of a sample solution (both without the use of a separating column) may be preferred over on-line liquid chromatography-mass spectometry in certain applications. Electrospray or ionspray is applicable to polar or ionic samples. Weakly polar and apolar samples are not ionized under electrospray or ionspray conditions. Applications of the techniques are in the fields of drug metabolism, natural product analysis and the determination of high molecular weights through the observation of multiply charged ions. PMID:1686612

Bruins, A P

1991-08-21

351

Structure and structural diversity in resinites as determined by pyrolysis-gas chromatography-mass spectrometry  

SciTech Connect

Pyrolysis-gas chromatography-mass spectroscopy (Py-GC-MS) is a useful technique for the rapid characterization of resinites, especially when used in conjunction with in-situ methylation procedures, which permit chromatographic analysis of acidic components without complex sample preparation. Although significant diversity exists in resinite structures, the majority of resinites may be classified into one of three basic structural groups. Resinites from the largest and most important of these may be further subdivided on the basis of specific structural characteristics into three subclasses. Within these classes, details of specific composition may vary significantly between samples as a consequence of differences in botanical origin and/or level of maturation, but sufficient common structural characteristics exist within these classes to validate application of such a classification system. 13 refs., 3 figs., 1 tab.

Anderson, K.B.; Winans, R.E.

1991-01-01

352

Identification of tartary buckwheat tea aroma compounds with gas chromatography-mass spectrometry.  

PubMed

Tartary buckwheat tea, which is an important and healthy product, has a distinct malty aroma. However, its characteristic aroma compounds have not been elucidated. The aims of present study were identification and quantification of its aroma compounds. The analyses were performed by gas chromatography-mass spectrometry (GC-MS) after 3 different isolation techniques. Seventy-seven compounds were identified. Among these compounds, 35 were quantified by available standards. The compounds with a high probability of contribution to the tartary buckwheat tea aroma (OAV ? 10) were as follows: 2,5-dimethyl-4-hydroxy-3(2H)-furanone, nonanal, 2,3-diethyl-5-methylpyrazine, benzeneacetaldehyde, maltol, 2,5-dimethylpyrazine, 2-ethyl-5-methylpyrazine, trimethylpyrazine. Some nutritional and bioactive compounds were also identified in this study, such as linoleic acid, niacin, vanillic acid, 7-hydroxycoumarin, butylated hydroxytoluene. Practical Application: Tartary buckwheat, one type of buckwheat, has gained much attention from nutritionists and medical doctors in recent years. It is rich in rutin, quercetin, and other nutrients that are good for health. Tartary buckwheat-based product such as tartary buckwheat tea is an important and popular healthy product in China, Japan,South Korea, European countries as well as in American countries. It has a distinct malty aroma. The present study first identified and quantified of its aroma compounds. The results will draw attention to other researchers in food flavor and buckwheat filed. PMID:22417522

Qin, Peiyou; Ma, Tingjun; Wu, Li; Shan, Fang; Ren, Guixing

2011-08-01

353

Gas chromatography mass spectrometry based metabolic profiling reveals biomarkers involved in rice-gall midge interactions.  

PubMed

The Asian rice gall midge (Orseolia oryzae Wood-Mason) is a serious pest of rice that causes huge loss in yield. While feeding inside the susceptible host, maggots secrete substances that facilitate the formation of a hollow tube-like structure called gall and prevent panicle formation. The present investigation was carried out to get an account of biochemical changes occurring in the rice plant upon gall midge feeding. Metabolic profiling of host tissues from three rice varieties, namely, TN1, Kavya, and RP2068, exposed to gall midge biotype 1 (GMB1), was carried out using gas chromatography mass spectrometry (GC-MS). TN1 and GMB1 represented compatible interaction, while Kavya and GMB1 as well as RP2068 and GMB1 represented incompatible interactions. The current study identified several metabolites that could be grouped as resistance, susceptibility, infestation, and host features based on their relative abundance. These may be regarded as biomarkers for insect-plant interaction in general and rice-gall midge interaction in particular. PMID:25059749

Agarrwal, Ruchi; Bentur, Jagadish Sanmallappa; Nair, Suresh

2014-09-01

354

The gas chromatography/mass spectrometry can be used for dose estimation in irradiated pork  

NASA Astrophysics Data System (ADS)

Food safety can be improved using ionizing radiation to reduce food spoilage and to extend its shelf life. The gas chromatography/mass spectrometry (GC/MS) has been validated by the European Community as a powerful method to identify irradiated food containing fat. The preliminary goals of our research were: (i) to set up this method, based on the detection of radiation induced 2-dodecylcyclobutanones (2-DCB) in pork muscle samples and (ii) to check the microbiological efficacy of the treatment. The main objective was to render the GC/MS a quantitative technique for dose estimation, through the measurement of the 2-DCB concentration in the irradiated sample. Our results show that the reduction of the microbial population is substantially reduced even at 2 kGy, and that a clear identification of irradiated samples can be achieved also one month after irradiation at 2 kGy in frozen-stored samples. The 2-DCB concentration showed a linear dependence on dose in the range 1-10 kGy, no matter the origin of the sample; a unique calibration function was obtained, that allowed dose estimation in irradiated pork samples. A retrospective evaluation on the quality of the treatment could be carried out this way.

D'Oca, M. C.; Bartolotta, A.; Cammilleri, M. C.; Giuffrida, S. A.; Parlato, A.; Di Noto, A. M.; Caracappa, S.

2009-07-01

355

Ultra performance liquid chromatography - mass spectrometry studies of formalin-induced alterations of human brain lipidome.  

PubMed

The development of 'omics' sciences offers new opportunities for the study of neurodegenerative diseases but increases at the same time the sample demand on brain banks that collect and store valuable human post-mortem tissue. Our study aims to evaluate in lipidomics the potential of formalin-fixed tissue compared with the cryopreservation method, considered as the gold standard for biochemical research. Two complementary liquid chromatography/mass spectrometry analytical platforms were used on the basis of hybrid quadrupole time-of-flight and triple quadrupole mass spectrometers. Untargeted fingerprinting, semitargeted profiling of specific lipid classes and targeted monitoring of lipid species were performed in formalin-fixed and cryopreserved samples to provide detailed information at the molecular level on the formalin-induced alterations of the brain tissue. In vitro incubations of lipid standards were also performed to further describe the degradation processes induced by formaldehyde. Phospholipid compounds were found to be extensively hydrolysed, whilst the sphingolipid ones were preserved. N-methylation and N-formylation of amine-containing phospholipids have also been evidenced. These findings show that the potential detrimental effect of formalin on the analytes of interest must be taken into account when analysing formalin-fixed samples. PMID:25303393

Gaudin, Mathieu; Panchal, Maï; Ayciriex, Sophie; Werner, Erwan; Brunelle, Alain; Touboul, David; Boursier-Neyret, Claire; Auzeil, Nicolas; Walther, Bernard; Duyckaerts, Charles; Laprévote, Olivier

2014-10-01

356

Determination of free and ethoxylated alkylphenols in leather with gas chromatography-mass spectrometry.  

PubMed

An analytical approach was developed to determine nonylphenol (NP), octylphenol (OP), nonylphenol ethoxylates (NPEO(n)) and octylphenol ethoxylates (OPEO(n)) in leather samples involving the conversion of NPEO(n) and OPEO(n) into the corresponding NP and OP. The four targets were extracted from samples using ultrasonic-assisted acetonitrile extraction. NP and OP in the extracts were directly isolated with hexane and quantitatively determined with 4-n-nonylphenol as internal standard by gas chromatography-mass spectrometry (GC-MS). For NPEO(n) and OPEO(n) in the extracts, they were first converted into NP and OP with aluminum triiodide as cleavage agent, and the yielded NP and OP were determined by GC-MS. The contents of NPEO(n) and OPEO(n) were calculated by normalizing to NPEO(9) and OPEO(9), respectively. This method was properly validated and the real sample tests revealed the pollution significance of leather by NPEO(n) and OPEO(n). PMID:21067757

Ma, He-Wei; Cheng, Ya

2010-12-10

357

Determination of methomyl in the stomach contents of baited wildlife by gas chromatography-mass spectrometry.  

PubMed

The poisoning of wildlife with fly-bait containing the active ingredient methomyl is an intentional and illegal act in many jurisdictions. A case of 2 animals poisoned by methomyl through consumption of tainted bait at multiple stations is described. Although thermally and ultraviolet-labile, methomyl can be identified by gas chromatography-mass spectrometry and is detected in abundance in bait samples; however, it is not readily observed in tissues, owing to its rapid metabolism and elimination. The application of derivatizing functionalities, such as trimethylsilyl groups, stabilizes the methomyl-oxime metabolite to facilitate its detectability during exposure to the relatively harsh conditions of gas chromatography. This brief communication reports on the analytical detection of methomyl in baits and biological samples from poisoned wildlife. Essential to the case were the added determination of a fly-bait coactive ingredient, (Z)-9-tricosene, and identification of a chemical indicator, caffeine, to confirm both the type of pesticide product involved in the poisoning incident and the vehicle used to perpetrate its delivery. PMID:24105381

Buchweitz, John P; Bokhart, Mark; Johnson, Margaret; Lehner, Andreas

2013-11-01

358

Chemical Discrimination in Turbulent Gas Mixtures with MOX Sensors Validated by Gas Chromatography-Mass Spectrometry  

PubMed Central

Chemical detection systems based on chemo-resistive sensors usually include a gas chamber to control the sample air flow and to minimize turbulence. However, such a kind of experimental setup does not reproduce the gas concentration fluctuations observed in natural environments and destroys the spatio-temporal information contained in gas plumes. Aiming at reproducing more realistic environments, we utilize a wind tunnel with two independent gas sources that get naturally mixed along a turbulent flow. For the first time, chemo-resistive gas sensors are exposed to dynamic gas mixtures generated with several concentration levels at the sources. Moreover, the ground truth of gas concentrations at the sensor location was estimated by means of gas chromatography-mass spectrometry. We used a support vector machine as a tool to show that chemo-resistive transduction can be utilized to reliably identify chemical components in dynamic turbulent mixtures, as long as sufficient gas concentration coverage is used. We show that in open sampling systems, training the classifiers only on high concentrations of gases produces less effective classification and that it is important to calibrate the classification method with data at low gas concentrations to achieve optimal performance. PMID:25325339

Fonollosa, Jordi; Rodríguez-Luján, Irene; Trincavelli, Marco; Vergara, Alexander; Huerta, Ramón

2014-01-01

359

Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory - Determination of Wastewater Compounds by Polystyrene-Divinylbenzene Solid-Phase Extraction and Capillary-Column Gas Chromatography/Mass Spectrometry  

USGS Publications Warehouse

A method for the determination of 67 compounds typically found in domestic and industrial wastewater is described. The method was developed in response to increasing concern over the impact of endocrine-disrupting chemicals in wastewater on aquatic organisms. This method also may be useful for evaluating the impact of combined sanitary and storm-sewer overflow on the water quality of urban streams. The method focuses on the determination of compounds that are an indicator of wastewater or that have been chosen on the basis of their endocrine-disrupting potential or toxicity. These compounds include the alkylphenol ethoxylate nonionic surfactants and their degradates, food additives, fragrances, antioxidants, flame retardants, plasticizers, industrial solvents, disinfectants, fecal sterols, polycyclicaromatic hydrocarbons, and high-use domestic pesticides. Water samples are filtered to remove suspended particulate matter and then are extracted by vacuum through disposable solid-phase cartridges that contain polystyrene-divinylbenzene resin. Cartridges are dried with nitrogen gas, and then sorbed compounds are eluted with dichloromethane-diethyl ether (4:1) and determined by capillary-column gas chromatography/mass spectrometry. Recoveries in reagent-water samples fortified at 4 micrograms per liter averaged 74 percent ? 7 percent relative standard deviation for all method compounds. Initial method detection limits for single-component compounds (excluding hormones and sterols) averaged 0.15 microgram per liter. Samples are preserved by filtration, the addition of 60 grams NaCl, and storage at 4 degrees Celsius. The laboratory has established a sample-holding time (prior to sample extraction) of 14 days from the date of sample collection until a statistically accepted method can be used to determine the effectiveness of these sample-preservation procedures.

Zaugg, Steven D.; Smith, Steven G.; Schroeder, Michael P.; Barber, Larry B.; Burkhardt, Mark R.

2002-01-01

360

Disposition of the Herbicide 2-Chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine (Atrazine) and Its Major Metabolites in Mice: A Liquid Chromatography/Mass Spectrometry Analysis of Urine, Plasma, and Tissue Levels  

PubMed Central

2-Chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine (atrazine, ATR) is a toxicologically important and widely used herbicide. Recent studies have shown that it can elicit neurological, immunological, developmental, and biochemical alterations in several model organisms, including in mice. Because disposition data in mice are lacking, we evaluated ATR's metabolism and tissue dosimetry after single oral exposures (5–250 mg/kg) in C57BL/6 mice using liquid chromatography/mass spectrometry (Ross and Filipov, 2006). ATR was metabolized and cleared rapidly; didealkyl ATR (DACT) was the major metabolite detected in urine, plasma, and tissues. Plasma ATR peaked at 1 h postdosing and rapidly declined, whereas DACT peaked at 2 h and slowly declined. Most ATR and metabolite residues were excreted within the first 24 h. However, substantial amounts of DACT were still present in 25- to 48-h and 49- to 72-h urine. ATR reached maximal brain levels (0.06–1.5 ?M) at 4 h (5–125 mg/kg) and 1 h (250 mg/kg) after dosing, but levels quickly declined to <0.1 ?M by 12 h in all the groups. In contrast, strikingly high concentrations of DACT (1.5–50 ?M), which are comparable with liver DACT levels, were detectable in brain at 2 h. Brain DACT levels slowly declined, paralleling the kinetics of plasma DACT. Our findings suggest that in mice ATR is widely distributed and extensively metabolized and that DACT is a major metabolite detected in the brain at high levels and is ultimately excreted in urine. Our study provides a starting point for the establishment of models that link target tissue dose to biological effects caused by ATR and its in vivo metabolites. PMID:19116264

Ross, Matthew K.; Jones, Toni L.; Filipov, Nikolay M.

2009-01-01

361

Identifying Ca2+-binding sites in proteins by liquid chromatography-mass spectrometry using Ca2+-directed dissociations.  

PubMed

Here we describe a new method to identify calcium-binding sites in proteins using high-resolution liquid chromatography-mass spectrometry in concert with calcium-directed collision-induced dissociations. Our method does not require any modifications to the liquid chromatography-mass spectrometry apparatus, uses standard digestion protocols, and can be applied to existing high-resolution MS data files. In contrast to NMR, our method is applicable to very small amounts of complex protein mixtures (femtomole level). Calcium-bound peptides can be identified using three criteria: (1) the calculated exact mass of the calcium containing peptide; (2) specific dissociations of the calcium-containing peptide from threonine and serine residues; and (3) the very similar retention times of the calcium-containing peptide and the free peptide. PMID:25023127

Jamalian, Azadeh; Sneekes, Evert-Jan; Wienk, Hans; Dekker, Lennard J M; Ruttink, Paul J A; Ursem, Mario; Luider, Theo M; Burgers, Peter C

2014-11-01

362

Determination of amphetamine-type stimulants in oral fluid by solid-phase microextraction and gas chromatography–mass spectrometry  

Microsoft Academic Search

A method for the simultaneous identification and quantification of amphetamine (AMP), methamphetamine (MET), fenproporex (FEN), diethylpropion (DIE) and methylphenidate (MPH) in oral fluid collected with Quantisal™ device has been developed and validated. Thereunto, in-matrix propylchloroformate derivatization followed by direct immersion solid-phase microextraction and gas chromatography–mass spectrometry were employed. Deuterium labeled AMP was used as internal standard for all the stimulants

Daniele Z. Souza; Paula O. Boehl; Eloisa Comiran; Kristiane C. Mariotti; Flavio Pechansky; Paulina C. A. V. Duarte; Raquel De Boni; Pedro E. Froehlich; Renata P. Limberger

2011-01-01

363

Selected ion monitoring gas chromatography\\/mass spectrometry of 1,2-diacylglycerol tert -butyldimethylsilyl ethers derived from glycerophospholipids  

Microsoft Academic Search

Selected ion monitoring was used in conjunction with gas chromatography\\/mass spectrometry to analyzetert-butyldimethylsilyl ethers (tert-BDMS) of 1,2-diacyl-sn-glycerols derived from naturally occurring glycerophospholipids, including those ofEscherichia coli, soybean, egg yolks and porcine liver. First, the fatty acid composition of the unknown glycerophospholipid was determined\\u000a by gasliquid chromatography (GLC) and, based on that, the fatty acids (mostly >0.5 wt%) were selected for

Toshiaki Ohshima; Chiaki Koizumi

1991-01-01

364

Detection of biomarkers in the organic matter of rocks from the Romashkinskoe oil field using gas chromatography-mass spectrometry  

Microsoft Academic Search

Polycyclic hydrocarbons (biomarkers) were detected in the organic matter of Paleozoic and pre-Paleozoic rocks from the Romashkinskoe\\u000a oil field in the Volga-Ural region using gas chromatography-mass spectrometry. Coefficients were calculated from the ratio\\u000a between tetra- and pentacyclic hydrocarbons, and the facial genetic types, possible generation sources, and evolution transformation\\u000a conditions of the initial organic matter were determined from the array

N. S. Sharipova; G. K. Budnikov; B. V. Uspenskii; G. P. Kayukova

2010-01-01

365

Validation of an analytical procedure to measure trace amounts of neurosteroids in brain tissue by gas chromatography–mass spectrometry  

Microsoft Academic Search

A selective and extremely sensitive procedure has been developed and optimized, using high-performance liquid chromatography (HPLC), specific derivatization and gas chromatography–mass spectrometry (GC–MS), to simultaneously quantify very small amounts of different neurosteroids from rat brain. Unconjugated and sulfated steroids in brain extracts were separated by solid-phase extraction. The unconjugated fraction was further purified by HPLC, the steroids being collected in

Philippe Liere; Yvette Akwa; Sébastien Weill-Engerer; Bernard Eychenne; Antoine Pianos; Paul Robel; Jan Sjövall; Michaël Schumacher; Etienne-Emile Baulieu

2000-01-01

366

Identification of New Metabolites of Bacterial Transformation of Indole by Gas Chromatography-Mass Spectrometry and High Performance Liquid Chromatography  

PubMed Central

Arthrobacter sp. SPG transformed indole completely in the presence of an additional carbon source. High performance liquid chromatography and gas chromatography-mass spectrometry detected indole-3-acetic acid, indole-3-glyoxylic acid, and indole-3-aldehyde as biotransformation products. This is the first report of the formation of indole-3-acetic acid, indole-3-glyoxylic acid, and indole-3-aldehyde from indole by any bacterium. PMID:25548566

Arora, Pankaj Kumar

2014-01-01

367

Characterization of kenaf ( Hibiscus cannabinus) lignin by pyrolysis-gas chromatography-mass spectrometry in the presence of tetramethylammonium hydroxide  

Microsoft Academic Search

Pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) in the presence of tetramethylammonium hydroxide (TMAH) was applied to kenaf (Hibiscus cannabinus) fibers in order to clarify the chemical composition of in situ lignin. The core and bast samples obtained from the middle position of variety Chinpi-3 were pyrolyzed at 500°C for 4 s with TMAH. The core pyrogram revealed peaks retaining the structural attributes

Ken-ichi Kuroda; Akiko Izumi; Bibhuti B Mazumder; Yoshito Ohtani; Kazuhiko Sameshima

2002-01-01

368

Rapid identification of phenylenediamine isomers in henna hair dye products by gas chromatography?mass spectrometry (GC?MS)  

Microsoft Academic Search

This paper describes a gas chromatography?mass spectrometry (GC?MS) procedure for identification and quantitation of phenylenediamine isomers in eleven commercial and traditional henna hair dyes. Our results indicate that p?phenylenediamine (p?PD), the least toxic diamine isomer, is most commonly present in the hair dyes selected for this study. While relatively low levels of p?PD are observed in most commercial hair dyes,

Peter Krahn; Huda Hassan; Thomas Mahier; Afrozul Haq

1999-01-01

369

Determination of linear alkylbenzenes in fish tissue by gel permeation chromatography and gas chromatography–mass spectrometry  

Microsoft Academic Search

A gel permeation chromatographic (GPC) procedure is described for separation of the long-chain linear alkylbenzenes (LABs) from fish muscle tissues. This technique was found to remove the matrix interference significantly and thereby improve the sensitivity of detection of LABs in the extracts. Gas chromatography–mass spectrometry (GC–MS) was then used to quantitate LABs in different species of fish and also fish

M. Indira Venkatesan; Terrence Northrup; Charles R Phillips

2002-01-01

370

Fluoroacetylation/fluoroethylesterification as a derivatization approach for gas chromatography-mass spectrometry in metabolomics: preliminary study of lymphohyperplastic diseases.  

PubMed

Metabolic fingerprinting in combination with gas chromatography and multivariate analysis is being extensively employed for the improved understanding of biological changes induced by endogenous or exogenous factors. Chemical derivatization increases the sensitivity and specificity of gas chromatography-mass spectrometry (GC-MS) for polar or thermally labile biological compounds, which bear derivatizable groups. Thus, there is a constant demand for simple methods of derivatization and separation that satisfy the need for metabolite analysis, identifying as many chemical classes of compounds as possible. In this study, an optimized protocol of extraction and derivatization is established as a generally applicable method for the analysis of a wide range of classes of metabolites in urine, whole blood and saliva. Compounds of biological relevance bearing hydroxyl- carboxyl- and amino-groups are derivatized using single-step fluoroacetylation/fluoroethylesterification after proper optimization of the protocol. Subsequently, the developed derivatization procedure is engaged in finding blood metabolic biomarkers, induced by lymphohyperplastic disease, through the metabolomic fingerprinting approach, the multivariate modeling (hierarchical cluster analysis) and GC-MS. Our preliminary, GC-MS-based metabolomic fingerprinting study underlines the contribution of certain metabolites to the discrimination of patients with lymphohyperplastic diseases. PMID:23806352

Karamani, Anna A; Fiamegos, Yiannis Ch; Vartholomatos, George; Stalikas, Constantine D

2013-08-01

371

Determination of organoarsenic warfare agents in sediment samples from Skagerrak by gas chromatography-mass spectrometry.  

PubMed

In 1945 the Norwegian authorities gave permission to scuttle ships loaded with captured chemical ammunition on board in an area approximately 14x4 km in size, 25 nautical miles south-east of Arendal. An investigation was carried out in 2002 to inspect four wrecks by using a remote-operated vehicle with video cameras. The Norwegian Defence Research Establishment (Forsvarets forskningsinstitutt, FFI) carried out the project on behalf of the Norwegian Pollution Control Authority (SFT). Sediment samples were collected at eight positions around each wreck. One of the wrecks was broken up into several smaller parts. Here sediments were collected at one additional position close to one of the parts. From each position, at least two sediment cores were taken up to the surface. One of the cores from each position was sliced into three parts that were immediately frozen. The other whole cores were frozen on board the ship and transported back to the laboratory in a freezer. In total, sediment samples from 33 different locations were collected and analysed for organoarsenic warfare agents and some of their decomposition products by gas chromatography-mass spectrometry (GC-MS) after derivatisation with 1-propanethiol. Most of the identified organoarsenic compounds found in the sediment samples are parts of the arsine oil mixture produced by Germany during World War II. The compounds were found both close to the wreck and at a somewhat longer distance from the wrecks. The highest concentrations were found in a sediment sample collected close to a bomb seen on the seabed. The organoarsenic warfare agents adamsite or lewisite were not found in any of the samples. Lewisite is not reported to have been produced during World War II, but was nevertheless looked for in the samples. PMID:15993928

Tørnes, John Aasulf; Opstad, Aase Mari; Johnsen, Bjørn Arne

2006-03-01

372

Determination of nitrogen-15 enrichment of nitrate and nitrite using thermospray liquid chromatography-mass spectrometry  

SciTech Connect

A new method has been developed for the determination of percent /sup 15/N enrichment in NO/sub 2//sup -/ and NO/sub 3//sup -/ that is both rapid and sensitive. NO/sub 2//sup -/ and NO/sub 3//sup -/ separation was done by use of reverse-phase liquid chromatography with a mobile phase consisting of ammonium acetate with tetrabutylammonium acetate as the ion pair reagent. The % /sup 15/N in isotopically enriched anions was determined by using thermospray liquid chromatography-mass spectrometry (LC-MS). Enrichment values were obtained on as little as 20 ng of NO/sub 2//sup -/-N/20 ..mu..L and 4 ng of NO/sub 3//sup -/-N/20 ..mu..L. The linear regression curve was plotted for the observed enrichment vs. the actual enrichment over the range from the natural abundance to 25% enrichment for each anion and the equation for the linear regression calculated (y = 1.16x + 0.7577 for NO/sub 2//sup -/ and y = 0.951x + 0.447 for NO/sub 3//sup -/). The coefficient of determination for the NO/sub 2//sup -/ and NO/sub 3//sup -/ curves was 0.988 and 0.987, respectively. The dynamic range of the method was found to be suitable for the range of NO/sub 2//sup -/ and NO/sub 3//sup -/ expected in plant xylem sap. Xylem sap samples obtained from NO/sub 3//sup -/ fed pea, Pisum sativum cv. Homesteader (3.9 ..mu..g of NO/sub 3//sup -/-N/mL, 24.7% /sup 15/N), contained a /sup 15/N enrichment of 25.4% +/- 0.7%.

Hogge, L.R.; Hynes, R.K.; Nelson, L.M.; Vestal, M.L.

1986-11-01

373

Determination of bullatacin in rat plasma by liquid chromatography-mass spectrometry.  

PubMed

A liquid chromatography-mass spectrometry method has been developed and validated for the quantification of bullatacin, a bistetrahydrofuran annonaceous acetogenin, in rat plasma. Squamostatin-A was selected as the internal standard. Analytes were extracted from rat plasma by liquid/liquid extraction using ethyl acetate with high efficiency. The chromatographical separation was performed on an Agilent Zorbax SB-C?? column (150 mm × 2.1 mm, 5 ?m). The mobile phase consisted of methanol and deionized water (95:5, v/v) containing 0.01% (v/v) formic acid. The chromatographic run time was 7 min per injection and flow rate was 0.2 mL/min. The retention time was 3.22 and 5.23 min for internal standard and bullatacin, respectively. The elutes were detected under positive electrospray ionization and the target analytes quantified by selected ion monitoring mode (645.9 m/z for bullatacin and 661.9 m/z for squamostatin-A). The method was sensitive with the limit of quantitation at 0.5 ng/mL in 100 ?L of rat plasma. Good linearity (r²=0.9998) was obtained covering the concentration of 0.5-2000 ng/mL. The intra- and inter-day assay precision ranged from 3.2 to 8.7% and 2.7 to 9.2%, respectively. In addition, the stability, extraction recovery and matrix effect involved in the method were also validated. This method was applied to measure the plasma bullatacin concentrations after a single tail vein intravenous administration of bullatacin in rats. PMID:22534655

Chen, Yong; Chen, Jian-wei; Liu, Shi-jia; Xu, Chun-lei; Xu, Hui-qing; Cai, Bao-chang; Li, Xiang; Ju, Wen-zheng

2012-05-15

374

Nitrate Reduction in a Groundwater Microcosm Determined by 15N Gas Chromatography-Mass Spectrometry  

PubMed Central

Aerobic and anaerobic groundwater continuous-flow microcosms were designed to study nitrate reduction by the indigenous bacteria in intact saturated soil cores from a sandy aquifer with a concentration of 3.8 mg of NO3?-N liter?1. Traces of 15NO3? were added to filter-sterilized groundwater by using a Darcy flux of 4 cm day?1. Both assimilatory and dissimilatory reduction rates were estimated from analyses of 15N2, 15N2O, 15NH4+, and 15N-labeled protein amino acids by capillary gas chromatography-mass spectrometry. N2 and N2O were separated on a megabore fused-silica column and quantified by electron impact-selected ion monitoring. NO3? and NH4+ were analyzed as pentafluorobenzoyl amides by multiple-ion monitoring and protein amino acids as their N-heptafluorobutyryl isobutyl ester derivatives by negative ion-chemical ionization. The numbers of bacteria and their [methyl-3H]thymidine incorporation rates were simultaneously measured. Nitrate was completely reduced in the microcosms at a rate of about 250 ng g?1 day?1. Of this nitrate, 80 to 90% was converted by aerobic denitrification to N2, whereas only 35% was denitrified in the anaerobic microcosm, where more than 50% of NO3? was reduced to NH4+. Assimilatory reduction was recorded only in the aerobic microcosm, where N appeared in alanine in the cells. The nitrate reduction rates estimated for the aquifer material were low in comparison with rates in eutrophic lakes and coastal sediments but sufficiently high to remove nitrate from an uncontaminated aquifer of the kind examined in less than 1 month. PMID:16348048

Bengtsson, Göran; Annadotter, Heléne

1989-01-01

375

Aging Alters Hepatic DNA Hydroxymethylation, as Measured by Liquid Chromatography/Mass Spectrometry  

PubMed Central

Background: Aging is one of the most important risk factors for cancer. It appears that aberrant epigenetic changes might be a common driver of aging and cancer. Among them are changes in DNA methylation and DNA hydroxymethylation. The 5? carbon of cytosines in CpG dinucleotides of DNA can be either methylated or hydroxymethylated. Like 5?-methylcytosine, changes in 5?-hydroxymethylcytosine may occur due to aging, potentially leading to downstream changes in transcription and cancer development. Methods: We set up a method to measure 5?-methyl-2?-deoxycytidine and 5?-hydroxymethyl-2?-deoxycytidine in DNA using liquid chromatography/mass spectrometry (LC/MS-MS) and used this method to measure the percentage of total cytosine that was either methylated or hydroxymethylated in the liver tissues of young and old C57Bl/6 male mice. The DNA was enzymatically hydrolyzed by sequential digestion with nuclease P1, phosphodiesterase I and alkaline phosphatase. The isotopomers [15N3]-2?-deoxycytidine and (methyl-d3, ring-6-d1)-5-methyl-2?-deoxycytidine were added to the DNA hydrolysates as internal standards. DNA methylation and hydroxymethylation were calculated as a percentage of total deoxycytidine in genomic DNA. Results: Within day variations for DNA methylation and hydroxymethylation were 3.45% and 8.40%, while day to day variations were 6.14% and 17.68%, respectively. Using this method it was determined that hepatic DNA of old mice had increased levels of hydroxymethylation relative to young (0.32 ± 0.02% vs. 0.24 ± 0.01%, P = 0.02), with no significant changes in 5?-methylcytosine. Conclusions: DNA hydroxymethylation measured by LC/MS-MS method can be a novel biomarker of aging. It will be useful to investigate the potential role of DNA hydroxymethylation in the development and prevention of age-associated cancer. PMID:25574465

Tammen, Stephanie A.; Dolnikowski, Gregory G.; Ausman, Lynne M.; Liu, Zhenhua; Kim, Kyong-chol; Friso, Simonetta; Choi, Sang-Woon

2014-01-01

376

Determination of endogenous ethanol in blood and breath by gas chromatography-mass spectrometry.  

PubMed

We describe methods for the determination of endogenous ethanol in biological specimens from healthy abstaining subjects. The analytical methods were headspace gas chromatography (GC) for plasma samples and gas chromatography-mass spectometry (GC/MS) with deuterium labelled species 2H3-ethanol and 2H5-ethanol as internal standards for breath analysis. Ethanol in rebreathed air was about 10% higher than in directly analysed end-expired alveolar air. Known volumes of rebreathed air were passed through a liquid-N2 freeze trap and the volatile constituents of breath were concentrated prior to analysis by GC or GC/MS. Besides endogenous ethanol, peaks were seen on the chromatograms for methanol, acetone and acetaldehyde as well as several as yet unidentified substances. The endogenous alcohols ethanol and methanol were confirmed from their mass chromatograms and the GC/MS profile also indicated the presence of endogenous propan-1-ol. The concentration of endogenous ethanol in plasma showed wide inter-subject variations ranging from below detection limits to 1.6 micrograms/ml (34.8 mumol/l) and with mean +/- SD of 0.39 +/- 0.45 micrograms/ml (8.5 +/- 9.8 mumol/l). We aim to characterise further the role of endogenous ethanol with the main focus on dynamic aspects such as the rate of formation and turnover. PMID:6634839

Jones, A W; Mårdh, G; Anggård, E

1983-01-01

377

A multi-fiber handling device for in vivo solid phase microextraction-liquid chromatography-mass spectrometry applications.  

PubMed

Solid phase microextraction, an in vivo and ex vivo sample preparation method, continues to capture growing interest among researchers for bioanalytical applications. When coupled with liquid chromatography mass spectrometry, the procedure often involves large numbers of fibers in, for example, both pharmacokinetic and pharmadynamic studies as well as other bioapplications. In this regard, appropriate and adequate precaution will be critical in preventing the fibers firstly from any possible external contamination and damage to maintain high analytical data integrity. In addition, improving the offline desorption of fibers specifically for in vivo SPME will not only help in improving data quality, but will also significantly decrease the overall analysis time. This article introduces a prototype multi-fiber handling device capable of simultaneous extraction/desorption of multiple solid phase microextraction (SPME) fibers on a 96-deep well plate format. This device thus provides an alternative approach to improving higher sample throughput for in vivo SPME liquid chromatography mass spectrometry applications. The portable design of the device ensures effective protection and prevention of fibers against damage and possible contamination and thus maintains analytical data reliability. To ensure its suitability for parallel extraction/desorption, the device was carefully evaluated using four benzodiazepines (diazepam, nordiazepam, oxazepam and lorazepam) as model drugs by monitoring inter- and intra-well variability. The effect of agitation speed on data precision and accuracy, effect of device weight on data precision, and comparison of the overall performance of the device with traditional manual desorption approach were also assessed. Results obtained from evaluation of the device with particular focus on the desorption process indicated that the weight of the device has no effect on the reliability and reproducibility of data acquired using the device. The average amount of diazepam obtained for 20 selected wells with and without device was 48.8pg and 49.4pg, respectively. Intra-, inter-well, and inter fiber variations recorded were all ?13% indicating an excellent precision and reproducibility can be attained with the device. PMID:22078236

Cudjoe, Erasmus; Pawliszyn, Janusz

2012-04-01

378

Detection of aldehydes in lung cancer cell culture by gas chromatography/mass spectrometry and solid-phase microextraction with on-fiber derivatization  

E-print Network

Aldehydes in lung cancer cell culture have been investigated using gas chromatography/mass spectrometry and solid-phase microextraction with on-fiber derivatization. In this study, the poly(dimethylsiloxane/divinylbenzene (PDMS/DVB) fiber was used...

Shan, Guangqing

2007-09-17

379

[Determination of migration of 25 primary aromatic amines from food contact plastic materials by gas chromatography-mass spectrometry].  

PubMed

A solid phase extraction (SPE) combination with gas chromatography-mass spectrometry (GC-MS) was developed for the determination of the migration of 25 primary aromatic amines (PAAs) from food contact plastic materials and articles. The samples were extracted by deionized water and 30 g/L acetic acid, and the pH value of the solution was adjusted to 8 - 10 with ammonia. The extracts were cleaned up and concentrated on an SPE column, then eluted by equal volume of methyl-tert-butyl ether and ethanol. The analysis of the target compounds was performed by GC-MS. The results indicated that the limits of detection were in the range of 0.4 -2.0 microg/kg for different PAAs. The recoveries and relative standard deviations (n = 7) of 10 microg/kg PAAs ranged from 51.6% -118.4% and 0.5% -9.8%, respectively, except the 2,4-diaminoanisole in the acid simulant. The effects of different experimental conditions such as the pH value and volume ratio of methyl-tert-butyl ether and ethanol were studied. The results showed that the method is accurate and stable, and could meet the requirement of the European Commission Regulation (EU) No 10/2011 for the determination of primary aromatic amines. It can be applied in the analysis of the primary aromatic amines in real food contact plastic material and article samples. PMID:23667989

Li, Ying; Li, Chengfa; Xiao, Daoqing; Liang, Feng; Chen, Zhinan; Schen, Xuhui; Sun, Xiaoying; Li, Yongtao

2013-01-01

380

A gas chromatography-mass spectrometry based study on serum metabolomics in rats chronically poisoned with hydrogen sulfide.  

PubMed

Hydrogen sulfide poisoning is a common occupational hazard, whose mortality and incidence rates are first and second, respectively, among occupational poisoning incidents in China. The main target organs of its toxicity are in the central nervous system and respiratory system. However, there are currently no specific direct tests that can be used to diagnose poisoned patients. In this study, we developed a serum metabonomic method using orthogonal partial least squares-discriminate analysis (OPLS-DA), based on gas chromatography-mass spectrometry (GC/MS) to evaluate the effect of chronic poisoning by hydrogen sulfide in rats. The OPLS-DA data demonstrated that the model group (n = 60) differed significantly from the control group (n = 30), suggesting that the metabolic profiles of the two groups are markedly different. Alterations in the levels of some metabolites such as citrate, galactose, lactate, mannose, inositol, urea, phosphate, alanine and valine were detected by OPLS-DA analysis. We observed changes in metabolic pathways including lipid metabolism, energy metabolism and amino metabolism in the model group. Our results indicate that GC/MS-based metabonomic methods may provide novel detection means for chronic hydrogen sulfide poisoning. PMID:25882152

Deng, Mingjie; Zhang, Meiling; Huang, Xueli; Ma, Jianshe; Hu, Lufeng; Lin, Guanyang; Wang, Xianqin

2015-05-01

381

[Development of a gas chromatography-mass spectrometry method for the metabolomic study of rice (Oryza sativa L.) grain].  

PubMed

An analytical strategy for the metabolic profiling of rice grain was developed based on gas chromatography-mass spectrometry (GC-MS). For the purpose of obtaining abundant metabolite information, sample preparation step prior to instrumental analysis is necessary to be optimized. D-optimal experimental design was applied to optimize the extraction solvent. Four solvents, including water, methanol, isopropanol and acetonitrile, and their combinations were evaluated for the extraction efficiency using multivariate statistical analysis (partial least square regression). The count of resolved peaks and the sum of peak areas were taken as the evaluation indexes. Methanol/water (80:20, v/v) mixture was highly efficient for rice metabolites and was selected as the suitable solvent formulation. Then, the analytical characteristics of the method were measured. More than 90% of the metabolites had satisfactory precisions, reproducibilities and stabilities (relative standard deviations (RSDs) < 30%). Most of the detected metabolites (about 88.0% of total peak area) showed good linear responses. With the optimized analytical protocol, 315 metabolites were detected in rice and 86 of which were structurally identified by searching in the NIST 08/Wiley standard mass spectral library, covering carbohydrates, amino acids, organic acids, steroids and so on which showed a broad coverage of metabolite data. The established method is expected to be useful for the metabolomic studies of rice. PMID:23383493

Zhou, Jia; Wang, Shuangyuan; Chang, Yuwei; Zhao, Yanni; Lu, Xin; Zhao, Chunxia; Xu, Guowang

2012-10-01

382

Characterization of aroma compounds of Chinese famous liquors by gas chromatography-mass spectrometry and flash GC electronic-nose.  

PubMed

Aroma composition of five Chinese premium famous liquors with different origins and liquor flavor types was characterized by gas chromatography-mass spectrometry (GC-MS) and flash gas chromatographic electronic nose system. Eighty-six aroma compounds were identified, including 5 acids, 34 esters, 10 alcohols, 9 aldehydes, 4 ketones, 4 phenols, and 10 nitrous and sulfuric compounds. To investigate possible correlation between aroma compounds identified by GC-MS and sensory attributes, multivariate ANOVA-PLSR (APLSR) was performed. It turned out that there were 30 volatile composition, ethyl acetate, ethyl propanoate, ethyl 2-methyl butanoate, ethyl 3-methyl butanoate, ethyl lactate, ethyl benzenacetate, 3-methylbutyl acetate, hexyl acetate, 3-methyl-1-butanol, 1-heptanol, phenylethyl alcohol, acetaldehyde, 1,1-diethoxy-3-methyl butane, furfural, benzaldehyde, 5-methyl-2-furanal, 2-octanone, 2-n-butyl furan, dimethyl trisulfied and 2,6-dimethyl pyrazine, ethyl nonanoate, isopentyl hexanoate, octanoic acid, ethyl 5-methyl hexanoate, 2-phenylethyl acetate,ethyl oleate, propyl hexanoate, butanoic acid and phenol, ethyl benzenepropanoate, which showed good coordination with Chinese liquor characteristics. The multivariate structure of this electronic nose responses was then processed by principal component analysis (PCA) and hierarchical cluster analysis (HCA). According to the obtained results, GC-MS and electronic nose can be used for the differentiation of the liquor origins and flavor types. PMID:24333641

Xiao, Zuobing; Yu, Dan; Niu, Yunwei; Chen, Feng; Song, Shiqing; Zhu, Jiancai; Zhu, Guangyong

2014-01-15

383

Plasma Metabolite Profiling and Chemometric Analyses of Lung Cancer along with Three Controls through Gas Chromatography-Mass Spectrometry  

PubMed Central

Lung cancer has been the most common death causing cancer in the world for several decades. This study is focused on the metabolite profiling of plasma from lung cancer (LC) patients with three control groups including healthy non-smoker (NS), smokers (S) and chronic obstructive pulmonary disease patients (COPD) samples using gas chromatography-mass spectrometry (GC-MS) in order to identify the comparative and distinguishing metabolite pattern for lung cancer. Metabolites obtained were identified through National Institute of Standards and Technology (NIST) mass spectral (Wiley registry) and Fiehn Retention Time Lock (RTL) libraries. Mass Profiler Professional (MPP) Software was used for the alignment and for all the statistical analysis. 32 out of 1,877 aligned metabolites were significantly distinguished among three controls and lung cancer using p-value ? 0.001. Partial Least Square Discriminant Analysis (PLSDA) model was generated using statistically significant metabolites which on external validation provide high sensitivity (100%) and specificity (78.6%). Elevated level of fatty acids, glucose and acids were observed in lung cancer in comparison with control groups apparently due to enhanced glycolysis, gluconeogenesis, lipogenesis and acidosis, indicating the metabolic signature for lung cancer. PMID:25712604

Musharraf, Syed Ghulam; Mazhar, Shumaila; Choudhary, Muhammad Iqbal; Rizi, Nadeem; Atta-ur-Rahman

2015-01-01

384

Plasma Metabolite Profiling and Chemometric Analyses of Lung Cancer along with Three Controls through Gas Chromatography-Mass Spectrometry.  

PubMed

Lung cancer has been the most common death causing cancer in the world for several decades. This study is focused on the metabolite profiling of plasma from lung cancer (LC) patients with three control groups including healthy non-smoker (NS), smokers (S) and chronic obstructive pulmonary disease patients (COPD) samples using gas chromatography-mass spectrometry (GC-MS) in order to identify the comparative and distinguishing metabolite pattern for lung cancer. Metabolites obtained were identified through National Institute of Standards and Technology (NIST) mass spectral (Wiley registry) and Fiehn Retention Time Lock (RTL) libraries. Mass Profiler Professional (MPP) Software was used for the alignment and for all the statistical analysis. 32 out of 1,877 aligned metabolites were significantly distinguished among three controls and lung cancer using p-value ? 0.001. Partial Least Square Discriminant Analysis (PLSDA) model was generated using statistically significant metabolites which on external validation provide high sensitivity (100%) and specificity (78.6%). Elevated level of fatty acids, glucose and acids were observed in lung cancer in comparison with control groups apparently due to enhanced glycolysis, gluconeogenesis, lipogenesis and acidosis, indicating the metabolic signature for lung cancer. PMID:25712604

Musharraf, Syed Ghulam; Mazhar, Shumaila; Choudhary, Muhammad Iqbal; Rizi, Nadeem; Atta-Ur-Rahman

2015-01-01

385

Determination of Volatile Compounds in Four Commercial Samples of Japanese Green Algae Using Solid Phase Microextraction Gas Chromatography Mass Spectrometry  

PubMed Central

Green algae are of great economic importance. Seaweed is consumed fresh or as seasoning in Japan. The commercial value is determined by quality, color, and flavor and is also strongly influenced by the production area. Our research, based on solid phase microextraction gas chromatography mass spectrometry (SPME-GC-MS), has revealed that volatile compounds differ intensely in the four varieties of commercial green algae. Accordingly, 41 major volatile compounds were identified. Heptadecene was the most abundant compound from Okayama (Ulva prolifera), Tokushima (Ulva prolifera), and Ehime prefecture (Ulva linza). Apocarotenoids, such as ionones, and their derivatives were prominent volatiles in algae from Okayama (Ulva prolifera) and Tokushima prefecture (Ulva prolifera). Volatile, short chained apocarotenoids are among the most potent flavor components and contribute to the flavor of fresh, processed algae, and algae-based products. Benzaldehyde was predominant in seaweed from Shizuoka prefecture (Monostroma nitidum). Multivariant statistical analysis (PCA) enabled simple discrimination of the samples based on their volatile profiles. This work shows the potential of SPME-GC-MS coupled with multivariant analysis to discriminate between samples of different geographical and botanical origins and form the basis for development of authentication methods of green algae products, including seasonings. PMID:24592162

Yoshikawa, Keisuke; Fujita, Akira; Mase, Nobuyuki; Watanabe, Naoharu

2014-01-01

386

Headspace-trap gas chromatography-mass spectrometry for determination of sulphur mustard and related compounds in soil.  

PubMed

Methods for trace determination of sulphur mustard (HD) and some related cyclic sulphur compounds in soil samples have been developed using headspace-trap in combination with gas chromatography-mass spectrometry (GC-MS). Two quite different types of soil were employed in the method optimisation (sandy loam and silty clay loam). Prior to analysis, water saturated with sodium chloride was added to the samples, at a water to soil ratio of 1:1. A detection limit of 3 ng/g was achieved for HD, while the cyclic sulphur compounds 1,4-thioxane, 1,3-dithiolane and 1,4-dithiane could be detected at 0.2-0.7 ng/g. The methods were validated in the concentration range from the limit of quantification (LOQ) to hundred times LOQ. The within assay precision at fifty times LOQ was 6.9-7.3% relative standard deviation (RSD) for determination of the cyclic sulphur compounds, and 15% RSD for determination of HD. Recoveries were in the range of 43-60% from the two soil types. As the technique requires very little sample preparation, the total time for sample handling and analysis was less than 1h. The technique was successfully employed for the determination of cyclic sulphur compounds in a sediment sample from an old dumping site for chemical munitions, known to contain HD degradation products. PMID:20189185

Røen, Bent T; Unneberg, Erik; Tørnes, John Aa; Lundanes, Elsa

2010-04-01

387

PRECISION AND ACCURACY IN THE DETERMINATION OF ORGANICS IN WATER BY FUSED SILICA CAPILLARY COLUMN GAS CHROMOTOGRAPHY/MASS SPECTROMETRY AND PACKED COLUMN GAS CHROMATOGRAPHY/MASS SPECTROMETRY  

EPA Science Inventory

Two general methods for the identification and measurement of organic compounds in water are compared. One method employs packed column chromatography and the other fused silica capillary column chromatography. The two gas chromatography/mass spectrometry (GC/MS) methods use diff...

388

Sequential derivatization of polar organic compounds in cloud water using O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride, N,O-bis(trimethylsilyl)trifluoroacetamide, and gas-chromatography/mass spectrometry analysis.  

PubMed

Cloud water samples from Whiteface Mountain, NY were used to develop a combined sampling and gas chromatography-mass spectrometric (GCMS) protocol for evaluating the complex mixture of highly polar organic compounds (HPOC) present in this atmospheric medium. Specific HPOC of interest were mono- and di keto-acids which are thought to originate from photochemical reactions of volatile unsaturated hydrocarbons from biogenic and manmade emissions and be a major fraction of atmospheric carbon. To measure HPOC mixtures and the individual keto-acids in cloud water, samples first must be derivatized for clean elution and measurement, and second, have low overall background of the target species as validated by GCMS analysis of field and laboratory blanks. Here, we discuss a dual derivatization method with PFBHA and BSTFA which targets only organic compounds that contain functional groups reacting with both reagents. The method also reduced potential contamination by minimizing the amount of sample processing from the field through the GCMS analysis steps. Once derivatized only gas chromatographic separation and selected ion monitoring (SIM) are needed to identify and quantify the polar organic compounds of interest. Concentrations of the detected total keto-acids in individual cloud water samples ranged from 27.8 to 329.3ngmL(-1) (ppb). Method detection limits for the individual HPOC ranged from 0.17 to 4.99ngmL(-1) and the quantification limits for the compounds ranged from 0.57 to 16.64ngmL(-1). The keto-acids were compared to the total organic carbon (TOC) results for the cloud water samples with concentrations of 0.607-3.350mgL(-1) (ppm). GCMS analysis of all samples and blanks indicated good control of the entire collection and analysis steps. Selected ion monitoring by GCMS of target keto-acids was essential for screening the complex organic carbon mixtures present at low ppb levels in cloud water. It was critical for ensuring high levels of quality assurance and quality control and for the correct identification and quantification of key marker compounds. PMID:25182854

Sagona, Jessica A; Dukett, James E; Hawley, Harmonie A; Mazurek, Monica A

2014-10-01

389

Simultaneous determination of 76 micropollutants in water samples by headspace solid phase microextraction and gas chromatography-mass spectrometry.  

PubMed

This study focuses on the development of an analytical method based on headspace solid phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of 76 micropollutants in water samples. The selected micropollutants include volatile organic compounds (VOCs) (e.g. chlorobenzenes, chloroalkanes), endocrine disrupting compounds (EDCs) (e.g. bisphenol A and tributyl phosphate), odour compounds (e.g. limonene, phenol), fragrance allergens (e.g. geraniol, eugenol) and some pesticides (e.g. heptachlor, terbutryn). The experimental conditions affecting their extraction, such as the type of fibre, temperature and time of extraction, sample volume and ionic strength of the samples were optimized using HS-SPME. The method showed good linear range, reproducibility between days, repeatability and low detection limits (at ng L(-1) levels). The validated method has been applied to determine the target organic micropollutants in aqueous samples from different experimental research units of surface water, sea water, waste water and those effluents of advance membrane treatments. The optimized method showed good performance in the different types of samples studied. The analysis revealed the presence of several micropollutants at concentrations between 20 and 5000 ?g L(-1), such as ethylbenzene, o-xylene, p-isopropilbenzene, D-limonene, citral and isoeugenol, due to the fact that these species are commonly used in domestic and industrial applications. PMID:24148498

Martínez, C; Ramírez, N; Gómez, V; Pocurull, E; Borrull, F

2013-11-15

390

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

PubMed

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

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

2015-01-01

391

Liquid Chromatography/Mass Spectrometry Methods for Measuring Dipeptide Abundance in Non-Small Cell Lung Cancer  

PubMed Central

RATIONALE Metabolomic profiling is a promising methodology of identifying candidate biomarkers for disease detection and monitoring. Although lung cancer is among the leading causes of cancer-related mortality worldwide, the lung tumor metabolome has not been fully characterized. METHODS We utilized a targeted metabolomic approach to analyze discrete groups of related metabolites. We adopted a dansyl [5-(dimethylamino)-1-napthalene sulfonamide] derivatization with liquid chromatography/ mass spectrometry (LC/MS) to analyze changes of metabolites from paired tumor and normal lung tissues. Identification of dansylated dipeptides was confirmed with synthetic standards. A systematic analysis of retention times (RT) was required to reliably identify isobaric dipeptides. We validated our findings in a separate sample cohort. RESULTS We produced a database of the LC retention time and MS/MS spectra of 361 dansyl dipeptides. Interpretation of the spectra is presented. Using this standard data, we identified a total of 279 dipeptides in lung tumor tissue. The abundance of 90 dipeptides was selectively increased in lung tumor tissue compared to normal tissue. In a second set of validation tissues, 12 dipeptides were selectively increased. CONCLUSIONS A systematic evaluation of certain metabolite classes in lung tumors may identify promising disease-specific metabolites. Our database of all possible dipeptides will facilitate ongoing translational applications of metabolomic profiling as it relates to lung cancer. PMID:23943330

Fitch, William L.; Zheng, Ming; Merritt, Robert E.; Shrager, Joseph B.; Zhang, Weiruo; Dill, David L.; Peltz, Gary; Hoang, Chuong D.

2013-01-01

392

Gas Chromatography- Mass Spectrometry Based Metabolomic Approach for Optimization and Toxicity Evaluation of Earthworm Sub-Lethal Responses to Carbofuran  

PubMed Central

Despite recent advances in understanding mechanism of toxicity, the development of biomarkers (biochemicals that vary significantly with exposure to chemicals) for pesticides and environmental contaminants exposure is still a challenging task. Carbofuran is one of the most commonly used pesticides in agriculture and said to be most toxic carbamate pesticide. It is necessary to identify the biochemicals that can vary significantly after carbofuran exposure on earthworms which will help to assess the soil ecotoxicity. Initially, we have optimized the extraction conditions which are suitable for high-throughput gas chromatography mass spectrometry (GC-MS) based metabolomics for the tissue of earthworm, Metaphire posthuma. Upon evaluation of five different extraction solvent systems, 80% methanol was found to have good extraction efficiency based on the yields of metabolites, multivariate analysis, total number of peaks and reproducibility of metabolites. Later the toxicity evaluation was performed to characterize the tissue specific metabolomic perturbation of earthworm, Metaphire posthuma after exposure to carbofuran at three different concentration levels (0.15, 0.3 and 0.6 mg/kg of soil). Seventeen metabolites, contributing to the best classification performance of highest dose dependent carbofuran exposed earthworms from healthy controls were identified. This study suggests that GC-MS based metabolomic approach was precise and sensitive to measure the earthworm responses to carbofuran exposure in soil, and can be used as a promising tool for environmental eco-toxicological studies. PMID:24324663

Saxena, Prem Narain

2013-01-01

393

Rapid determination of polysaccharides in BianTi Soft Extract by spectrophotometry coupled with gas chromatography-mass spectrometry  

PubMed Central

A simple approach for the rapid determination of polysaccharides in BianTi Soft Extract using spectrophotometry coupled with gas chromatography-mass spectrometry (GC-MS) was developed. The mixed standard solution composed of D-glucose, D-mannose, galactose and D-xylose in different proportions (1.00: 1.01: 0.12: 0.05) was prepared according to the monosaccharide composition analysis of the polysaccharides by GC-MS. The determination of polysaccharides by UV-Vis spectrophotometer was performed after 35-min color reaction, in which 1 ml 5% phenol and 4 ml sulfate was used. The assay of the method validation has shown that the method was stable, reliable and feasible. Furthermore, the proposed method was successfully applied in the preparation procedure of BianTi Soft Extract, selecting out optimal decoction conditions and suitable decoction container. It suggests that the convenient method could be useful for the quality control of BianTi Soft Extract. Meanwhile, it may be an alternative for polysaccharides determination of other formulations. PMID:20668575

Zheng, Minxia; Shen, Jie; Yang, Kai; Qian, Songxiang; Feng, Sujuan

2010-01-01

394

New pilot for validation of automated analyses of organics by gas chromatography mass spectrometry (GCMS): application to space researches  

NASA Astrophysics Data System (ADS)

The search for complex organic molecules in extraterrestrial environments, including important biomolecules such as amino acids and carboxylic acids, will require after an extraction a derivatization step to transform these organic compounds into species that are sufficiently volatile to be detected by gas chromatography mass spectrometry (GCMS). Current and future space missions, such as Mars Science Laboratory (MSL 2011, will include such derivatization method and thus a dedicated laboratory pilot is needed to validate protocols before launch of the probes. A new in situ generic Derivatization-Pyrolysis Unit (DPU) is presented. Derivatization is carried out in a 4 mL reactor placed on a GCMS injector for automated derivatization as well as for pre- and post treatment of the sample. The DPU unit is evaluated in terms of its technical features. The performances are illustrated with applications including conventional and in situ derivatization for using terrestrial Mars analog materials enriched by a 5 nmol amino acids solution. The DPU allows the analysis of a wide range of molecules to be detected and can be adapted to samples from any solid spatial object such as Mars, asteroids and comets. This pilot is a good basis for the validation of future generations of instruments, such as the Mars Organic Molecule Analyzer (MOMA) of the Exomars 2018 mission, dedicated to the search for organics in spatial environments.

Sternberg, Robert; Buch, Arnaud; Chazalnoel, Pascale; Geffroy, Claude; David, Marc

395

A serum metabolomic investigation on lipoprotein lipase-deficient mice with hyperlipidemic pancreatitis using gas chromatography/mass spectrometry.  

PubMed

Hypertriglyceridemia (HTG) is often associated with acute pancreatitis. The relationship between these diseases and the role that hypertriglyceridemia plays in acute pancreatitis pathogenesis remains to be elucidated. In the present study, in order to investigate the mechanisms of hyper-lipidemic acute pancreatitis (HLP), we established an animal model using lipoprotein lipase (LPL)-deficient heterozygous mice injected with caerulein. Susceptibility to pancreatitis in LPL-deficient heterozygous mice was compared with that of wild-type mice after intraperitoneal (i.p.) injections of caerulein by determining amylase release and pancreatic pathological scores. Furthermore, serum metabolome was detected through chemical derivatization followed by gas chromatography/mass spectrometry (GC/MS). GC/MS data were analyzed by orthogonal-projection to latent structures-discriminant analysis (OPLS-DA). Caerulein induced increased levels of serum amylase and more severe pancreatic inflammation in LPL-deficient mice compared to wild-type mice. HLP was discriminated more accurately from healthy controls by the metabolites, including valine, leucine and citrate. The metabolites included valine, leucine, citrate, malic acid, proline, tetradecanoic acid (14:0), glutamine and oleic acid (18:1). Changes in energy, fat and amino acid metabolism were also evident. In conclusion, LPL-deficient heterozygous mice with hypertriglyceridemia (HTG) exhibited enhanced susceptibility to acute pancreatitis. GC/MS data revealed differences between healthy and HLP mice. Therefore, this technique is novel and a useful tool for the study of the HLP pathogenetic mechanism. PMID:24648970

Tang, Maochun; Hu, Gouyong; Zhao, Yan; Su, Mingming; Wang, Yuhui; Jia, Wei; Qiu, Yunping; Liu, George; Wang, Xingpeng

2013-05-01

396

Metabolic Toxicity Screening Using Electrochemiluminescence Arrays Coupled with Enzyme-DNA Biocolloid Reactors and Liquid Chromatography-Mass Spectrometry  

NASA Astrophysics Data System (ADS)

New chemicals or drugs must be guaranteed safe before they can be marketed. Despite widespread use of bioassay panels for toxicity prediction, products that are toxic to a subset of the population often are not identified until clinical trials. This article reviews new array methodologies based on enzyme/DNA films that form and identify DNA-reactive metabolites that are indicators of potentially genotoxic species. This molecularly based methodology is designed in a rapid screening array that utilizes electrochemiluminescence (ECL) to detect metabolite-DNA reactions, as well as biocolloid reactors that provide the DNA adducts and metabolites for liquid chromatography-mass spectrometry (LC-MS) analysis. ECL arrays provide rapid toxicity screening, and the biocolloid reactor LC-MS approach provides a valuable follow-up on structure, identification, and formation rates of DNA adducts for toxicity hits from the ECL array screening. Specific examples using this strategy are discussed. Integration of high-throughput versions of these toxicity-screening methods with existing drug toxicity bioassays should allow for better human toxicity prediction as well as more informed decision making regarding new chemical and drug candidates.

Hvastkovs, Eli, G.; Schenkman, John B.; Rusling, James, F.

2012-07-01

397

Comparison of gas chromatography/mass spectrometry and immunoassay techniques on concentrations of atrazine in storm runoff  

USGS Publications Warehouse

Gas chromatography/mass spectrometry (GC/MS) and enzyme linked immunosorbent assay (ELISA) techniques were used to measure concentrations of dissolved atrazine in 149 surface-water samples. Samples were collected during May 1992-September 1993 near the mouth of the White River (Indiana) and in two small tributaries of the river. GC/MS was performed on a Hewlett- Packard 5971A with electron impact ionization and selected ion monitoring of filtered water samples extracted by C-18 solid phase extraction: ELISA was performed with a magnetic-particle-based assay with photometric analysis. ELISA results compared reasonably well to GC/MS measurements at concentrations below the Maximum Contaminant Level for drinking water set by the U.S. Environmental Protection Agency (3.0 ??g/L), but a systematic negative bias was observed at higher concentrations. When higher concentration samples were diluted into the linear range of calibration, the relation improved. A slight positive bias was seen in all of the ELISA data compared to the GC/MS results, and the bias could be partially explained by correcting the ELISA data for cross reactivity with other triazine herbicides. The highest concentrations of atrazine were found during the first major runoff event after the atrazine was applied. Concentrations decreased throughout the rest of the sampling period even though large runoff events occurred during this time, indicating that most atrazine loading to surface waters in the study area occurs within a few weeks after application.

Lydy, M.J.; Carter, D.S.; Crawford, C.G.

1996-01-01

398

Characterization of important odorants in steamed male Chinese mitten crab (Eriocheir sinensis) using gas chromatography-mass spectrometry-olfactometry.  

PubMed

Chinese mitten crab (Eriocheir sinensis) from Yangcheng Lake in Jiangsu Province is a popular species due to its unique pleasant aroma and intensive umami taste. In this study, odorants in steamed male E. sinensis were investigated using the headspace-monolithic material sorptive extraction technique coupled with gas chromatography-mass spectrometry-olfactometry (GC-MS-O). A total of 74 volatile compounds were found, and the results of the GC-MS-O analysis, combined with odor activity values, showed that trimethylamine (fishy, ammonia-like odor), (Z)-4-heptenal (mushroom-like odor), and benzaldehyde (paint-like odor) were the important odorants (IOs) in all 4 of the edible parts of steamed male E. sinensis. Furthermore, heptanal (mushroom-like odor) was common to the abdomen, claw, and leg meat but was not found as the IO in the gonad. The abdomen meat also contained 3-methylbutanal (vegetable-like, grassy odor), while 2 additional IOs were found in claw meat (2-methylbutanal, which has a mushroom odor and 3-ethyl-2,5-dimethylpyrazine, which has a chocolate-like, musty odor). Another IO (2-nonanone, chocolate-like odor) was also found in leg meat, while (E)-2-nonenal (green, fruity odor) was the IO found exclusively in the gonad. PMID:24962135

Wu, Na; Gu, Saiqi; Tao, Ningping; Wang, Xichang; Ji, Siru

2014-07-01

399

Metabolic Toxicity Screening Using Electrochemiluminescence Arrays Coupled with Enzyme-DNA Biocolloid Reactors and Liquid Chromatography–Mass Spectrometry  

PubMed Central

New chemicals or drugs must be guaranteed safe before they can be marketed. Despite widespread use of bioassay panels for toxicity prediction, products that are toxic to a subset of the population often are not identified until clinical trials. This article reviews new array methodologies based on enzyme/DNA films that form and identify DNA-reactive metabolites that are indicators of potentially genotoxic species. This molecularly based methodology is designed in a rapid screening array that utilizes electrochemiluminescence (ECL) to detect metabolite-DNA reactions, as well as biocolloid reactors that provide the DNA adducts and metabolites for liquid chromatography–mass spectrometry (LC-MS) analysis. ECL arrays provide rapid toxicity screening, and the biocolloid reactor LC-MS approach provides a valuable follow-up on structure, identification, and formation rates of DNA adducts for toxicity hits from the ECL array screening. Specific examples using this strategy are discussed. Integration of high-throughput versions of these toxicity-screening methods with existing drug toxicity bioassays should allow for better human toxicity prediction as well as more informed decision making regarding new chemical and drug candidates. PMID:22482786

Hvastkovs, Eli G.; Schenkman, John B.; Rusling, James F.

2012-01-01

400

Characterisation and discrimination of various types of lac resin using gas chromatography mass spectrometry techniques with quaternary ammonium reagents.  

PubMed

A variety of lac resin samples obtained from artists' suppliers, industrial manufacturers, and museum collections were analysed using gas chromatography mass spectrometry (GCMS) and reactive pyrolysis GCMS with quaternary ammonium reagents. These techniques allowed a detailed chemical characterisation of microgram-sized samples, based on the detection and identification of derivatives of the hydroxy aliphatic and cyclic (sesquiterpene) acids that compose the resin. Differences in composition could be related to the nature of the resin, e.g. wax-containing (unrefined), bleached, or aged samples. Furthermore, differences in the relative abundances of aliphatic hydroxyacids appear to be associated with the biological source of the resin. The diagnostic value of newly characterised lac components, including 8-hydroxyacids, is discussed here for the first time. Identification of derivatised components was aided by AMDIS deconvolution software, and discrimination of samples was enhanced by statistical evaluation of data using principal component analysis. The robustness of the analyses, together with the minimal sample size required, make these very powerful approaches for the characterisation of lac resin in museum objects. The value of such analyses for enhancing the understanding of museum collections is illustrated by two case studies of objects in the collection of the Philadelphia Museum of Art: a restorer's varnish on a painting by Luca Signorelli, and a pictorial inlay in an early nineteenth-century High Chest by George Dyer. PMID:24642395

Sutherland, K; del Río, J C

2014-04-18

401

[Determination of chlorophenol and pyrethroid preservatives in wooden furniture by solid phase extraction coupled with gas chromatography-mass spectrometry].  

PubMed

A method for the determination of 10 wood preservatives of chlorophenols (2,4-dichlorophenol, 2, 4, 6-trichlorophenol, 2, 4, 5-trichlorophenol, 2, 3, 4, 6-tetrachlorophenol, pentachlorophenol, lindane) and pyrethroids (permethrin, cyfluthrin, cypermethrin, delta-methrin) in furniture by solid phase extraction (SPE) coupled with gas chromatography-mass spectrometry (GC-MS) was developed. The furniture samples were extracted twice by ultrasonic extraction in methanol. The extract was then evaporated and acetylated by the acetic anhydride and potassium carbonate. Finally the reaction solution was purified by Oasis HLB SPE column. The wood preservatives were eluted by ethyl acetate and collected for analysis by GC-MS. The ten wood preservatives can be separated and determined successfully by this method. Under the optimized conditions, the detection limits of the six chlorophenol compounds were 1 mg/kg, and the four pyrethroid compounds were 5 mg/kg, and the spiked recoveries of the 10 wood preservatives in samples were in the range of 76.0% - 108.8%. Forty commercial wooden furniture samples were tested and lindane was found in some samples. The results showed that the method is accurate, rapid and sensitive. It can be effectively used to analyze the wood preservatives in wooden furniture. PMID:23016294

Li, Haiyu; Zhang, Qing; Kang, Suyuan; Lü, Qing; Bai, Hua; Wang, Chao

2012-06-01

402

Accuracy profile validation of a new analytical method for propane measurement using headspace-gas chromatography-mass spectrometry.  

PubMed

Propane can be responsible for several types of lethal intoxication and explosions. Quantifying it would be very helpful to determine in some cases the cause of death. Some gas chromatography-mass spectrometry (GC-MS) methods of propane measurements do already exist. The main drawback of these GC-MS methods described in the literature is the absence of a specific propane internal standard necessary for accurate quantitative analysis. The main outcome of the following study was to provide an innovative Headspace-GC-MS method (HS-GC-MS) applicable to the routine determination of propane concentration in forensic toxicology laboratories. To date, no stable isotope of propane is commercially available. The development of an in situ generation of standards is thus presented. An internal-labeled standard gas (C?DH?) is generated in situ by the stoichiometric formation of propane by the reaction of deuterated water (D?O) with Grignard reagent propylmagnesium chloride (C?H?MgCl). The method aims to use this internal standard to quantify propane concentrations and, therefore, to obtain precise measurements. Consequently, a complete validation with an accuracy profile according to two different guidelines, the French Society of Pharmaceutical Sciences and Techniques (SFSTP) and the Gesellschaft für toxikologische und Forensische Chemie (GTFCh), is presented. PMID:24327620

Smith, Fiona; Augsburger, Marc; Varlet, Vincent

2014-03-01

403

Oligosaccharide Substrate Preferences of Human Extracellular Sulfatase Sulf2 Using Liquid Chromatography-Mass Spectrometry Based Glycomics Approaches  

PubMed Central

Sulfs are extracellular endosulfatases that selectively remove the 6-O-sulfate groups from cell surface heparan sulfate (HS) chain. By altering the sulfation at these particular sites, Sulfs function to remodel HS chains. As a result of the remodeling activity, HSulf2 regulates a multitude of cell-signaling events that depend on interactions between proteins and HS. Previous efforts to characterize the substrate specificity of human Sulfs (HSulfs) focused on the analysis of HS disaccharides and synthetic repeating units. In this study, we characterized the substrate preferences of human HSulf2 using HS oligosaccharides with various lengths and sulfation degrees from several naturally occurring HS sources by applying liquid chromatography mass spectrometry based glycomics methods. The results showed that HSulf2 preferentially digests highly sulfated HS oligosaccharides with zero acetyl groups and this preference is length dependent. In terms of length of oligosaccharides, HSulf2 digestion induced more sulfation decrease on DP6 (DP: degree of polymerization) compared to DP2, DP4 and DP8. In addition, the HSulf2 preferentially digests the oligosaccharide domain located at the non-reducing end (NRE) of the HS and heparin chain. In addition, the HSulf2 digestion products were altered only for specific isomers. HSulf2 treated NRE oligosaccharides also showed greater decrease in cell proliferation than those from internal domains of the HS chain. After further chromatographic separation, we identified the three most preferred unsaturated hexasaccharide for HSulf2. PMID:25127119

Huang, Yu; Mao, Yang; Buczek-Thomas, Jo Ann; Nugent, Matthew A.; Zaia, Joseph

2014-01-01

404

Unexpected dimerization of isoprene in a gas chromatography inlet. A study by gas chromatography/mass spectrometry coupling.  

PubMed

During analysis of pure isoprene by gas chromatography/mass spectrometry (GC-MS) using a programmed temperature vaporization (PTV) inlet, the presence of several isoprene dimers was detected in the total ion chromatograms (TICs). This study intends to determine the part of the instrument where dimerization occurs and the relative importance of the dimer amounts under different experimental conditions. The reference thermal dimerization of isoprene gives four six-membered cyclic dimers and two eight-membered ones. In all samples containing different amounts of freshly distilled isoprene, only peaks corresponding to the former appeared in TICs. For the same temperature, their amounts increase as the concentration of injected isoprene increases. The main products are diprene (from 80 to 100%) of the total dimers and dipentene (from 1 to 14%). The sum of the two other dimers is never higher than 6%. In conclusion, isomeric dimers are produced through a dimerization in the inlet. No dimerization of isoprene occurs in the mass spectrometer source. Then care is needed when analyzing terpenic compounds in the presence of isoprene by GC-MS because structures, retention times and mass spectra of diprene and dipentene are close. PMID:24485537

Estevez, Yannick; Gardrat, Christian; Berthelot, Karine; Grau, Etienne; De Jeso, Bernard; Ouardad, Samira; Peruch, Frédéric

2014-02-28

405

Determination of midazolam and its metabolite as a probe for cytochrome P450 3A4 phenotype by liquid chromatography–mass spectrometry  

Microsoft Academic Search

This study demonstrated the analysis of midazolam and its metabolites by liquid chromatography–mass spectrometry (LC–MS) with a sonic spray ionization (SSI) interface. The analytical column was a YMC-Pak Pro C18 (50mm×2.0mm i.d.) using 10mM ammonium acetate (pH 4.8)–methanol (1:1) at a flow rate of 0.2mlmin?1. The drift voltage was 100V. The sampling aperture was heated at 110°C and the shield

Hideko Kanazawa; Akiko Okada; Eri Igarashi; Megumu Higaki; Takako Miyabe; Tadashi Sano; Ryouhei Nishimura

2004-01-01

406

Detecting Organic Compounds in Martian Soil Analogues Using Gas Chromatography Mass Spectrometry  

NASA Technical Reports Server (NTRS)

One of the primary objectives of the 1976 Viking missions was to determine whether organic compounds, possibly of biological origin, were present in the Martian surface soils. The Viking gas chromatography mass spectrometry (GCMS) instruments found no evidence for any organic compounds of Martian origin above a few parts per billion in the upper 10 cm of surface soil [l], suggesting the absence of a widely distributed Martian biota. However, Benner et d. have suggested that significant amounts of non-volatile organic compounds, possibly including oxidation products of bioorganic molecules (e.g. carboxylic acids) would not have been detected by the Viking GCMS [2]. Moreover, other key organic compounds important to biology, such as amino acids and nucleobases, would also likely have been missed by the Viking GCMS as these compounds require chemical derivatization to be stable in a GC column [3]. Recent pyrolysis experiments with a Mars soil analogue that had been innoculated with Escherichia coli bacteria have shown that amino acid decomposition products (amines) and nucleobases are among the most abundant products generated after pyrolysis of the bacterial cells [4,5]. At the part per billion level (Viking GCMS detection limit), these pyrolysis products generated from several million bacterial cells per gram of Martian soil would not have been detected by the Viking GCMS instruments [4]. Analytical protocols are under development for upcoming in situ lander opportunities to target several important biological compounds including amino acids and nucleobases. For example, extraction and chemical derivatization techniques [3] are being adapted for space flight use to transform reactive or fragile molecules that would not have been detected by the Viking GCMS instruments, into species that are sufficiently volatile to be detected by GCMS. Recent experiments carried out at NASA Goddard have shown that using this derivatization technique all of the targeted compounds mentioned above can be separated on a GC column and detected by MS at sub-picomole (< 10(exp -l2 mole) levels. With these methods, the detection limit for amino acids, carboxylic acids and nucleobases is several orders of magnitude more sensitive than the Viking GCMS instruments for these compounds. Preliminary results using this analytical technique on a variety of Martian soil analogues will be presented.

Glavin, D. P.; Buch, A.; Mahaffy, P. R.

2004-01-01

407

Liquid chromatography mass spectrometry for quantifying plasma lysophospholipids: potential biomarkers for cancer diagnosis.  

PubMed

Cancer is a complex disease with many genetic and epigenetic aberrations that result in development of tumorigenic phenotypes. While many factors contribute to the etiology of cancer, emerging da