Analysis of poly-beta-hydroxybutyrate in environmental samples by GC-MS/MS.

Science.gov (United States)

Elhottová, D; Tríska, J; Petersen, S O; Santrůcková, H

2000-05-01

Application of gas chromatography-mass spectrometry (GC-MS) can significantly improve trace analyses of compounds in complex matrices from natural environments compared to gas chromatography only. A GC-MS/MS technique for determination of poly-beta-hydroxybutyrate (PHB), a bacterial storage compound, has been developed and used for analysis of two soils stored for up to 319 d, fresh samples of sewage sludge, as well as a pure culture of Bacillus megaterium. Specific derivatization of beta-hydroxybutyrate (3-OH C4:0) PHB monomer units by N-tert-butyl-dimethylsilyl-N-methyltrifluoracetamide (MTBSTFA) improved chromatographic and mass spectrometric properties of the analyte. The diagnostic fragmentation scheme of the derivates tert-butyldimethylsilyl ester and ether of beta-hydroxybutyric acid (MTBSTFA-HB) essential for the PHB identification was shown. The ion trap MS was used, therefore the scan gave the best sensitivity and with MS/MS the noise decreased, so the S/N was better and also with second fragmentation the amount of ions increased compared to SIM. The detection limit for MTBSTFA-HB by GC-MS/MS was about 10(-13) g microL(-1) of injected volume, while by GC (FID) and GC-MS (scan) it was around 10(-10) g microL(-1) of injected volume. Sensitivity of GC-MS/MS measurements of PHB in arable soil and activated sludge samples was down to 10 pg of PHB g(-1) dry matter. Comparison of MTBSTFA-HB detection in natural soil sample by GC (FID), GC-MS (scan) and by GC-MS/MS demonstrated potentials and limitations of the individual measurement techniques.

Qualitative and quantitative analysis of pyrolysis oil by gas chromatography with flame ionization detection and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry.

Science.gov (United States)

Sfetsas, Themistoklis; Michailof, Chrysa; Lappas, Angelos; Li, Qiangyi; Kneale, Brian

2011-05-27

Pyrolysis oils have attracted a lot of interest, as they are liquid energy carriers and general sources of chemicals. In this work, gas chromatography with flame ionization detector (GC-FID) and two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS) techniques were used to provide both qualitative and quantitative results of the analysis of three different pyrolysis oils. The chromatographic methods and parameters were optimized and solvent choice and separation restrictions are discussed. Pyrolysis oil samples were diluted in suitable organic solvent and were analyzed by GC×GC-TOFMS. An average of 300 compounds were detected and identified in all three samples using the ChromaToF (Leco) software. The deconvoluted spectra were compared with the NIST software library for correct matching. Group type classification was performed by use of the ChromaToF software. The quantification of 11 selected compounds was performed by means of a multiple-point external calibration curve. Afterwards, the pyrolysis oils were extracted with water, and the aqueous phase was analyzed both by GC-FID and, after proper change of solvent, by GC×GC-TOFMS. As previously, the selected compounds were quantified by both techniques, by means of multiple point external calibration curves. The parameters of the calibration curves were calculated by weighted linear regression analysis. The limit of detection, limit of quantitation and linearity range for each standard compound with each method are presented. The potency of GC×GC-TOFMS for an efficient mapping of the pyrolysis oil is undisputable, and the possibility of using it for quantification as well has been demonstrated. On the other hand, the GC-FID analysis provides reliable results that allow for a rapid screening of the pyrolysis oil. To the best of our knowledge, very few papers have been reported with quantification attempts on pyrolysis oil samples using GC×GC-TOFMS most of which make use of the

Matching and optimization of combined 3DQIT and TOFMS

International Nuclear Information System (INIS)

Baril, M.

1999-01-01

Combination of Three Dimensional Quadrupole Ion Trap and Time Of Flight Mass Spectrometer is very interesting because they both rely on time though in a different manner. The 3DQIT can accumulate many ions of which the desired ions can be selected and kept for a very long period of time. Ions can subsequently be extracted in a short burst from the 3DQIT to be sent in a TOFMS. This process can be eased if the trapped ions are cooled by collisions with gas molecules inside the trap. We will discuss from the basic principles of physics what are the best conditions leading the maximum number of usable ions to penetrate in the TOFMS while keeping the resolving power at an acceptable level

Dynamic olfactometry and GC–TOFMS to monitor the efficiency of an industrial biofilter

Energy Technology Data Exchange (ETDEWEB)

Gutiérrez, M.C.; Martín, M.A. [University of Cordoba, Department of Inorganic Chemical and Chemical Engineering, Campus Universitario de Rabanales, Carretera N-IV, km 396, Edificio Marie Curie, 14071 Córdoba (Spain); Pagans, E.; Vera, L. [Odournet SL, Parc de Recerca UAB, Edificio Eureka, Espacio P2M2, 08193, Bellaterra, Cerdanyola del Vallès, Barcelona (Spain); García-Olmo, J. [NIR/MIR Spectroscopy Unit, Central Service for Research Support (SCAI), University of Cordoba, Campus de Rabanales, 14071 Cordoba (Spain); Chica, A.F., E-mail: afchica@uco.es [University of Cordoba, Department of Inorganic Chemical and Chemical Engineering, Campus Universitario de Rabanales, Carretera N-IV, km 396, Edificio Marie Curie, 14071 Córdoba (Spain)

2015-04-15

Biofiltration is the most widely used technique for eliminating odours in waste treatment plants. Volatile organic compounds (VOCs) are among the odorous compounds emitted by waste management plants, and serve as variables to measure odour emissions depending on the type of aeration process used. In this work, we assess the performance of an industrial-scale biofilter where composting is the main source of VOCs and odour emissions. Dynamic olfactometry is the sensorial technique used to determine odour concentration, while gas chromatography–time of flight-mass spectrometry (GC–TOFMS) is used to perform the chemical characterization. This work examines a total of 82 compounds belonging to 15 odorous families of VOCs, particularly mercaptans, sulphur-containing compounds, alcohols and terpenes, among others. Principal component analysis (PCA) is used to assess the influence of each of these families of VOCs on the total variance of the measure with regard to both the input and output flow of the biofilter. Finally, partial least-squares (PLS) regression is used to estimate the odour concentration in each of the samples taken at the inlet and outlet of the biofilter in each of the samples based on the chemical information provided by chromatographic analysis. The study shows that there is an adequate correlation (r = 0.9751) between real and estimated odour concentrations, both of which are expressed in European odour units per cubic metre (ou{sub E}·m{sup −3}). - Highlights: • Odour and VOC removal by industrial biofilter was evaluated. • Dynamic olfactometry and GC-TOF MS were the techniques used. • The compost aeration mode was considered in this study. • The influence of 15 VOC families on sample variance was demonstrated by PCA. • Odour concentration was predicted from selected chromatographic information by PLS.

Optimization of separation and detection conditions for the multiresidue analysis of pesticides in grapes by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry.

Science.gov (United States)

Banerjee, Kaushik; Patil, Sangram H; Dasgupta, Soma; Oulkar, Dasharath P; Patil, Shubhangi B; Savant, Rahul; Adsule, Pandurang G

2008-05-09

A comprehensive GCxGC-TOFMS method was optimized for multiresidue analysis of pesticides using a combination of a non-polar (RTX-5MS, 10 m x 0.18 mm x 0.2 microm) and a polar capillary column (TR-50MS, 1 m x 0.1 mm x 0.1 microm), connected in series through a dual stage thermal modulator. The method resolved the co-elution problems as observed in full scan one-dimensional GC-MS analysis and allowed chromatographic separation of 51 pesticides within 24 min run time with library-searchable mass spectrometric confirmation. Four pesticides, viz. chlorpyrifos-methyl, vinclozoline, parathion-methyl and heptachlor could be baseline separated on GCxGC, which were otherwise closely eluting and interfering each other's detection in 1D GC-MS run. Similarly, it could be possible to separate myclobutanil, buprofezin, flusilazole and oxyfluorfen on GCxGC. Although in 1D GC-MS, these closely eluting compounds could be identified through deconvolution algorithm and 'peak-find' option of the Chromatof software but the spectral purity significantly improved on GCxGC analysis. Thorough optimization was accomplished for the oven temperature programming, ion source temperature and GCxGC parameters like modulation period, duration of hot pulses, modulation-offset temperature, acquisition rate, etc. to achieve best possible separation of the test compounds. The limit of detection significantly improved by 2-12 times on GCxGC-TOFMS against GC-TOFMS because of sharper and narrower peak shapes. The method was tested for grape matrix after preparing the samples using previously described method and recoveries of the entire test pesticides were within 70-110% at 10 ng/g level of fortification. GCxGC-TOFMS was found to be an excellent technique for library-based screening of pesticides with high accuracy and sensitivity.

SPME GC/MS determination of organochlorine pesticides in water samples

Directory of Open Access Journals (Sweden)

Yerbolat Sailaukhanuly

2013-05-01

Full Text Available Headspace solid phase microextraction (HS-SPME in combination with gas chromatography and mass-spectrometry (GC/MS was studied for analysis of water samples. The organochlorine pesticides (OCPs, p,p'-DDT, p,p'-DDD, and p,p'-DDE were collected and analyzed by GC/MS. To select of effective fiber coatings four types of SPME fibers were examined and compared. The parameters effecting the efficiency of HS-SPME such as extraction and pre-incubation time and extraction temperature, effect of solvent nature, ionic strength were studied to obtain optimal parameters. The method was developed using spiked water samples in a concentration range  10 - 500 ng/L. The calibration curve was linear over the studied concentration range with r≥0.9925. The detection limits varied from 1.57 to 2.08 ng/L. An authentic water samples from contaminated lake with OCPs were analyzed by developed method.

Discovery and identification of a series of alkyl decalin isomers in petroleum geological samples.

Science.gov (United States)

Wang, Huitong; Zhang, Shuichang; Weng, Na; Zhang, Bin; Zhu, Guangyou; Liu, Lingyan

2015-07-07

The comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC × GC/TOFMS) has been used to characterize a crude oil and a source rock extract sample. During the process, a series of pairwise components between monocyclic alkanes and mono-aromatics have been discovered. After tentative assignments of decahydronaphthalene isomers, a series of alkyl decalin isomers have been synthesized and used for identification and validation of these petroleum compounds. From both the MS and chromatography information, these pairwise compounds were identified as 2-alkyl-decahydronaphthalenes and 1-alkyl-decahydronaphthalenes. The polarity of 1-alkyl-decahydronaphthalenes was stronger. Their long chain alkyl substituent groups may be due to bacterial transformation or different oil cracking events. This systematic profiling of alkyl-decahydronaphthalene isomers provides further understanding and recognition of these potential petroleum biomarkers.

Direct sample introduction-gas chromatography-mass spectrometry for the determination of haloanisole compounds in cork stoppers.

Science.gov (United States)

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

2016-12-02

A solventless analytical method is proposed for analyzing the compounds responsible for cork taint in cork stoppers. Direct sample introduction (DSI) is evaluated as a sample introduction system for the gas chromatography-mass spectrometry (GC-MS) determination of four haloanisoles (HAs) in cork samples. Several parameters affecting the DSI step, including desorption temperature and time, gas flow rate and other focusing parameters, were optimized using univariate and multivariate approaches. The proposed method shows high sensitivity and minimises sample handling, with detection limits of 1.6-2.6ngg -1 , depending on the compound. The suitability of the optimized procedure as a screening method was evaluated by obtaining decision limits (CCα) and detection capabilities (CCβ) for each analyte, which were found to be in 6.9-11.8 and 8.7-14.8ngg -1 , respectively, depending on the compound. Twenty-four cork samples were analysed, and 2,4,6-trichloroanisole was found in four of them at levels between 12.6 and 53ngg -1 . Copyright © 2016 Elsevier B.V. All rights reserved.

Use of REMPI-TOFMS for real-time measurement of trace aromatics during operation of aircraft ground equipment

Science.gov (United States)

Gullett, Brian; Touati, Abderrahmane; Oudejans, Lukas

Emissions of aromatic air toxics from aircraft ground equipment (AGE) were measured with a resonance enhanced multiphoton ionization-time of flight mass spectrometry (REMPI-TOFMS) system consisting of a pulsed solid state laser for photoionization and a TOFMS for mass discrimination. This instrument was capable of characterizing turbine emissions and the effect of varying load operations on pollutant production. REMPI-TOFMS is capable of high selectivity and low detection limits (part per trillion to part per billion) in real time (1 s resolution). Hazardous air pollutants and criteria pollutants were measured during startups and idle and full load operations. Measurements of compounds such as benzene, toluene, ethylbenzene, xylenes, styrene, and polycyclic aromatic hydrocarbons compared well with standard methods. Startup emissions from the AGE data showed persistent concentrations of pollutants, unlike those from a diesel generator, where a sharp spike in emissions rapidly declined to steady state levels. The time-resolved responses of air toxics concentrations varied significantly by source, complicating efforts to minimize these emissions with common operating prescriptions. The time-resolved measurements showed that pollutant concentrations decline (up to 5×) in a species-specific manner over the course of multiple hours of operation, complicating determination of accurate and precise emission factors via standard extractive sampling. Correlations of air toxic concentrations with more commonly measured pollutants such as CO or PM were poor due to the relatively greater changes in the measured toxics' concentrations.

Speciation of organotin compounds in environmental samples by GC-ICPMS

International Nuclear Information System (INIS)

Vahcic, M.; Milacic, R.; Scancar, J.

2009-01-01

Full text: Analytical procedure using 15 m GC column was applied for simultaneous speciation of OTCs in various environmental samples. Methyl-, butyl-, phenyl- and octyl- tin species were quantitatively determined. different extraction reagents and conditions were studied. OTCs species were derivatized by NaBEt 4 and extracted into isooctane or hexane. The applied analytical procedure considerably shortened analytical time and enabled simultaneous determination of 12 OTCs in environmental samples. (author)

Open Probe fast GC-MS - combining ambient sampling ultra-fast separation and in-vacuum ionization for real-time analysis.

Science.gov (United States)

Keshet, U; Alon, T; Fialkov, A B; Amirav, A

2017-07-01

An Open Probe inlet was combined with a low thermal mass ultra-fast gas chromatograph (GC), in-vacuum electron ionization ion source and a mass spectrometer (MS) of GC-MS for obtaining real-time analysis with separation. The Open Probe enables ambient sampling via sample vaporization in an oven that is open to room air, and the ultra-fast GC provides ~30-s separation, while if no separation is required, it can act as a transfer line with 2 to 3-s sample transfer time. Sample analysis is as simple as touching the sample, pushing the sample holder into the Open Probe oven and obtaining the results in 30 s. The Open Probe fast GC was mounted on a standard Agilent 7890 GC that was coupled with an Agilent 5977A MS. Open Probe fast GC-MS provides real-time analysis combined with GC separation and library identification, and it uses the low-cost MS of GC-MS. The operation of Open Probe fast GC-MS is demonstrated in the 30-s separation and 50-s full analysis cycle time of tetrahydrocannabinol and cannabinol in Cannabis flower, sub 1-min analysis of trace trinitrotoluene transferred from a finger onto a glass surface, vitamin E in canola oil, sterols in olive oil, polybrominated flame retardants in plastics, alprazolam in Xanax drug pill and free fatty acids and cholesterol in human blood. The extrapolated limit of detection for pyrene is Open Probe fast GC-MS is demonstrated in the analysis of heroin in its street drug powder. The use of Open Probe with the fast GC acting as a transfer line is demonstrated in <10-s analysis without separation of ibuprofen and estradiol. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

On-line combination of liquid chromatography and capillary gas chromatography : preconcentration and analysis of organic compounds in aqueous samples

NARCIS (Netherlands)

Noij, T.H.M.; Weiss, E.; Herps, T.; Cruchten, van H.; Rijks, J.A.

1988-01-01

This paper describes the design of a new, versatile, and low-cost on-line LC-GC interface that allows the fast and reliable introduction of large sample volumes onto a capillary GC column. The sample introduction procedure consists successively of: evaporation of the entire sample (LC fraction),

Solid phase extraction in combination with comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry for the detailed investigation of volatiles in South African red wines

NARCIS (Netherlands)

Weldegergis, B.T.; Crouch, A.M.; Górecki, T.; Villiers, de A.

2011-01-01

Comprehensive two-dimensional gas chromatography in combination with time-of-flight mass spectrometry (GC × GC–TOFMS) has been applied for the analysis of volatile compounds in three young South African red wines. In spite of the significant benefits offered by GC × GC–TOFMS for the separation and

The Application of Resonance-Enhanced Multiphoton Ionization Technique in Gas Chromatography Mass Spectrometry

Directory of Open Access Journals (Sweden)

Adan Li

2014-01-01

Full Text Available Gas chromatography resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (GC/REMPI-TOFMS using a nanosecond laser has been applied to analyze the 16 polycyclic aromatic hydrocarbons (PAHs. The excited-state lifetime, absorption characters, and energy of electronic states of the 16 PAHs were investigated to optimize the ionization yield. A river water sample pretreated by means of solid phase extraction was analyzed to evaluate the performance of the analytical instrument. The results suggested that REMPI is superior to electron impact ionization method for soft ionization and suppresses the background signal due to aliphatic hydrocarbons. Thus, GC/REMPI-TOFMS is a more reliable method for the determination of PAHs present in the environment.

The metabolism of 4-bromoaniline in the bile-cannulated rat: application of ICPMS ((79/81)Br), HPLC-ICPMS & HPLC-oaTOFMS.

Science.gov (United States)

Duckett, Catherine; McCullagh, Michael; Smith, Christopher; Wilson, Ian D

2015-01-01

1. An excretion balance study was performed following i.p. administration of 4-bromoaniline (50 mg kg(-1)) to bile-cannulated rats, using bromine-detected ((79/81)Br) ICPMS for quantification. Approximately 90% of the dose was recovered in urine (68.9 ± 3.6%) and bile (21.4 ± 1.4%) by 48 h post-administration. 2. HPLC-ICPMS ((79/81)Br) was used to selectively detect and profile the major urinary and biliary-excreted metabolites and determined that the 0-12 h urine contained at least 21 brominated metabolites with 19 bromine-containing peaks observed in the 6-12 h bile samples. 3. The urinary and biliary metabolites were subsequently profiled using HPLC-oaTOFMS. By exploiting the distinctive bromine isotope pattern ca. 60 brominated metabolites were detected in the urine in negative electrospray ionisation (ESI) mode while bile contained ca. 21. 4. While a large number of bromine-containing metabolites were detected, the profiles were dominated by a few major components with the bulk of the 4-bromoaniline-related material in urine accounted for by 4-bromoanaline O-sulfate (∼75% of the total by ICPMS, 84% by TOFMS). In bile a hydroxylated N-acetyl compound was the major metabolite detected, forming some ∼65% of the 4-bromoaniline-related material by ICPMS (37% by TOFMS).

Quantitative analysis of semivolatile organic compounds in selected fractions of air sample extracts by GC/MI-IR spectrometry

International Nuclear Information System (INIS)

Childers, J.W.; Wilson, N.K.; Barbour, R.K.

1990-01-01

The authors are currently investigating the capabilities of gas chromatography/matrix isolation infrared (GC/MI-IR) spectrometry for the determination of semivolatile organic compounds (SVOCs) in environmental air sample extracts. Their efforts are focused on the determination of SVOCs such as alkylbenzene positional isomers, which are difficult to separate chromatographically and to distinguish by conventional electron-impact ionization GC/mass spectrometry. They have performed a series of systematic experiments to identify sources of error in quantitative GC/MI-IR analyses. These experiments were designed to distinguish between errors due to instrument design or performance and errors that arise from some characteristic inherent to the GC/MI-IR technique, such as matrix effects. They have investigated repeatability as a function of several aspects of GC/MI IR spectrometry, including sample injection, spectral acquisition, cryogenic disk movement, and matrix deposition. The precision, linearity, dynamic range, and detection limits of a commercial GC/MI-IR system for target SVOCs were determined and compared to those obtained with the system's flame ionization detector. The use of deuterated internal standards in the quantitative GC/MI-IR analysis of selected fractions of ambient air sample extracts will be demonstrated. They will also discuss the current limitations of the technique in quantitative analyses and suggest improvements for future consideration

Time-resolved molecular characterization of organic aerosols by PILS + UPLC/ESI-Q-TOFMS

Science.gov (United States)

Zhang, X.; Dalleska, N. F.; Huang, D. D.; Bates, K. H.; Sorooshian, A.; Flagan, R. C.; Seinfeld, J. H.

2016-04-01

Real-time and quantitative measurement of particulate matter chemical composition represents one of the most challenging problems in the field of atmospheric chemistry. In the present study, we integrate the Particle-into-Liquid Sampler (PILS) with Ultra Performance Liquid Chromatography/Electrospray ionization Quadrupole Time-of-Flight High-Resolution/Mass Spectrometry (UPLC/ESI-Q-TOFMS) for the time-resolved molecular speciation of chamber-derived secondary organic aerosol (SOA). The unique aspect of the combination of these two well-proven techniques is to provide quantifiable molecular-level information of particle-phase organic compounds on timescales of minutes. We demonstrate that the application of the PILS + UPLC/ESI-Q-TOFMS method is not limited to water-soluble inorganic ions and organic carbon, but is extended to slightly water-soluble species through collection efficiency calibration together with sensitivity and linearity tests. By correlating the water solubility of individual species with their O:C ratio, a parameter that is available for aerosol ensembles as well, we define an average aerosol O:C ratio threshold of 0.3, above which the PILS overall particulate mass collection efficiency approaches ∼0.7. The PILS + UPLC/ESI-Q-TOFMS method can be potentially applied to probe the formation and evolution mechanism of a variety of biogenic and anthropogenic SOA systems in laboratory chamber experiments. We illustrate the application of this method to the reactive uptake of isoprene epoxydiols (IEPOX) on hydrated and acidic ammonium sulfate aerosols.

The metabolism of 4-bromoaniline in the bile-cannulated rat: application of ICPMS (79/81Br), HPLC-ICPMS & HPLC-oaTOFMS

Science.gov (United States)

Duckett, Catherine; McCullagh, Michael; Smith, Christopher; Wilson, Ian D

2015-01-01

Abstract 1. An excretion balance study was performed following i.p. administration of 4-bromoaniline (50 mg kg−1) to bile-cannulated rats, using bromine-detected (79/81Br) ICPMS for quantification. Approximately 90% of the dose was recovered in urine (68.9 ± 3.6%) and bile (21.4 ± 1.4%) by 48 h post-administration. 2. HPLC-ICPMS (79/81Br) was used to selectively detect and profile the major urinary and biliary-excreted metabolites and determined that the 0–12 h urine contained at least 21 brominated metabolites with 19 bromine-containing peaks observed in the 6–12 h bile samples. 3. The urinary and biliary metabolites were subsequently profiled using HPLC-oaTOFMS. By exploiting the distinctive bromine isotope pattern ca. 60 brominated metabolites were detected in the urine in negative electrospray ionisation (ESI) mode while bile contained ca. 21. 4. While a large number of bromine-containing metabolites were detected, the profiles were dominated by a few major components with the bulk of the 4-bromoaniline-related material in urine accounted for by 4-bromoanaline O-sulfate (∼75% of the total by ICPMS, 84% by TOFMS). In bile a hydroxylated N-acetyl compound was the major metabolite detected, forming some ∼65% of the 4-bromoaniline-related material by ICPMS (37% by TOFMS). PMID:25837688

A cheap and simple passive sampler using silicone rubber for the ...

African Journals Online (AJOL)

caffeine, personal care products, pharmaceuticals, pesticides and polycyclic aromatic hydrocarbons. Keywords: passive sampler, silicone rubber (PDMS) tubing, GCxGC-TOFMS, ..... concentrations may be derived by using performance reference compounds to determine in situ passive sampler sampling rates followed by ...

Two-dimensional gas chromatography-online hydrogenation for improved characterization of petrochemical samples.

Science.gov (United States)

Potgieter, H; Bekker, R; Govender, A; Rohwer, E

2016-05-06

The Fischer-Tropsch (FT) process produces a variety of hydrocarbons over a wide carbon number range and during subsequent product workup a large variety of synthetic fuels and chemicals are produced. The complexity of the product slate obtained from this process is well documented and the high temperature FT (HT-FT) process products are spread over gas, oil and water phases. The characterization of these phases is very challenging even when using comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC-TOFMS). Despite the increase in separation power, peak co-elution still occurs when samples containing isomeric compounds are analysed by comprehensive two dimensional GC. The separation of isomeric compounds with the same double bond equivalents is especially difficult since these compounds elute in a similar position on the GC×GC chromatogram and have identical molecular masses and similar fragmentation patterns in their electron ionization (EI) mass spectra. On-line hydrogenation after GC×GC separation is a possible way to distinguish between these isomeric compounds since the number of rings and alkene double bonds can be determined from the mass spectra of the compounds before and after hydrogenation. This paper describes development of a GC×GC method with post column hydrogenation for the determination of the backbone of cyclic/olefinic structures enabling us to differentiate between classes like dienes and cyclic olefins in complex petrochemical streams. Copyright © 2016 Elsevier B.V. All rights reserved.

Dual Source Time-of-flight Mass Spectrometer and Sample Handling System

Science.gov (United States)

Brinckerhoff, W.; Mahaffy, P.; Cornish, T.; Cheng, A.; Gorevan, S.; Niemann, H.; Harpold, D.; Rafeek, S.; Yucht, D.

We present details of an instrument under development for potential NASA missions to planets and small bodies. The instrument comprises a dual ionization source (laser and electron impact) time-of-flight mass spectrometer (TOF-MS) and a carousel sam- ple handling system for in situ analysis of solid materials acquired by, e.g., a coring drill. This DSTOF instrument could be deployed on a fixed lander or a rover, and has an open design that would accommodate measurements by additional instruments. The sample handling system (SHS) is based on a multi-well carousel, originally de- signed for Champollion/DS4. Solid samples, in the form of drill cores or as loose chips or fines, are inserted through an access port, sealed in vacuum, and transported around the carousel to a pyrolysis cell and/or directly to the TOF-MS inlet. Samples at the TOF-MS inlet are xy-addressable for laser or optical microprobe. Cups may be ejected from their holders for analyzing multiple samples or caching them for return. Samples are analyzed with laser desorption and evolved-gas/electron-impact sources. The dual ion source permits studies of elemental, isotopic, and molecular composition of unprepared samples with a single mass spectrometer. Pulsed laser desorption per- mits the measurement of abundance and isotope ratios of refractory elements, as well as the detection of high-mass organic molecules in solid samples. Evolved gas analysis permits similar measurements of the more volatile species in solids and aerosols. The TOF-MS is based on previous miniature prototypes at JHU/APL that feature high sensitivity and a wide mass range. The laser mode, in which the sample cup is directly below the TOF-MS inlet, permits both ablation and desorption measurements, to cover elemental and molecular species, respectively. In the evolved gas mode, sample cups are raised into a small pyrolysis cell and heated, producing a neutral gas that is elec- tron ionized and pulsed into the TOF-MS. (Any imaging

Characterization of Chemical Composition of Pericarpium Citri Reticulatae Volatile Oil by Comprehensive Two-Dimensional Gas Chromatography with High-Resolution Time-of-Flight Mass Spectrometry

Directory of Open Access Journals (Sweden)

Kunming Qin

2013-01-01

Full Text Available Pericarpium Citri Reticulatae (Chenpi in Chinese has been widely used as an herbal medicine in Korea, China, and Japan. Chenpi extracts are used to treat indigestion and inflammatory syndromes of the respiratory tract such as bronchitis and asthma. This thesis will analyze chemical compositions of Chenpi volatile oil, which was performed by comprehensive two-dimensional gas chromatography with high-resolution time-of-flight mass spectrometry (GC × GC-HR-TOFMS. One hundred and sixty-seven components were tentatively identified, and terpene compounds are the main components of Chenpi volatile oil, a significant larger number than in previous studies. The majority of the eluted compounds, which were identified, were well separated as a result of high-resolution capability of the GC × GC method, which significantly reduces, the coelution. β-Elemene is tentatively qualified by means of GC × GC in tandem with high-resolution TOFMS detection, which plays an important role in enhancing the effects of many anticancer drugs and in reducing the side effects of chemotherapy. This study suggests that GC × GC-HR-TOFMS is suitable for routine characterization of chemical composition of volatile oil in herbal medicines.

Chromatographic enhancement techniques for the analysis of persistent organic pollutants in environmental samples

Energy Technology Data Exchange (ETDEWEB)

Reiner, E.; Boden, A.; MacPherson, K.; Kolic, T. [Ontario Ministry of the Environment, Ottawa, Ontario (Canada); Dorman, F. [Restek Corporation, Belefonte, PA (United States); Cochran, J. [LECO Corporation, Las Vegas, NV (United States)

2004-09-15

A number of chromatographic enhancements can be made to improve resolution, reduce analysis times and increase peak capacity. Fast GC with TOFMS is able to deconvolute coeluting peaks with unique mass spectra separated by at least 150 ms. Analyte specific columns like Rtx-Dioxin2 can resolve all the 2,3,7,8 containing congeners except 1,2,3,7,8,9-HxCDF. This compound is typically present at the lowest concentration or not detected and makes up less than 1% of the TEQ. Comprehensive 2D GC can be used to separate a number of difficult coelutions for PCBs and other halogenated organics.

Comparison of LC-ESI-MS and GC-MS for the Analysis of a Synthetic Tabun Sample

National Research Council Canada - National Science Library

D'Agostino, Paul

2003-01-01

Packed capillary LC-ESI-MS and capillary column GC-MS were compared for the analysis of a synthetic tabun sample as each method has advantages for the analysis of samples containing chemical warfare...

Application of accelerator mass spectrometry to environmental research, Trial of GC-AMS

International Nuclear Information System (INIS)

Shibata, Yasuyuki

2003-01-01

The accelerator analysis facility of the National Institute for Environmental Studies, which aims to develop a new device capable of measuring "1"4C age for each compound, is promoting the study to establish the GC-AMS that combines two-dimensional gas chromatograph (GC) and accelerator mass spectrometry (AMS). The on-line GC-AMS system for the metabolic measurement of "1"4C-labeled compounds for medicinal biochemical research is a system, in which a GC-separated sample is continuously converted into CO_2 in a combustion tube and introduced directly to a gas ion source to continuously measure "1"4C. In the "1"4C detection experiment, the concentration of CO_2 gas was changed using a helium introduction line and a sample injection valve, and CO_2 gas plus helium gas were introduced into the gas ion source. As a result, it was found that the online GC-AMS has feasibility and high potential capability. For off-line GC-AMS for environmental samples, after purification with preparative gas chromatography, the sample is converted to graphite in a vacuum line and applied to common AMS measurement. The authors collected Northwest Pacific Ocean bottom sediment cores, and performed the extraction and purification of fatty acids of specific stratigraphy and the "1"4C measurement of each compound. The age of the compound derived from the surface layer planktons was the result capable of indicating the sedimentary age of the stratigraphy. In addition, as an application study to explore the source of pollutants in the environment using "1"4C as a tracer representing the characteristics of each source, the authors started to conduct the research choosing atmospheric dust samples. As a starting point, the authors attempted to measure the "1"4C concentration of vehicle exhaust particles and incinerator fly ash particles respectively. There was hardly any "1"4C in vehicle exhaust particles. (A.O.)

Statistical approach To understand MALDI-TOFMS matrices : discovery and evaluation of new MALDI matrices

NARCIS (Netherlands)

Meier, M.A.R.; Adams, N.; Schubert, U.S.

2007-01-01

A statistical approach is described to better understand the role of the matrix during a MALDI-TOFMS expt. Potential matrix mols. were selected based on a rational exptl. design and subsequently screened in order to investigate whether a certain compd. can act as a matrix for synthetic polymers. The

Forensic Characterization of Liquor Samples by Gas Chromatography-Mass Spectrometry (GC-MS – A Review

Directory of Open Access Journals (Sweden)

Praveen K. Yadav

2017-12-01

Full Text Available Alcohol is a subject of forensic research across the world. The forensic characterization of alcoholic beverages is required in cases of death and crimes due to alcohol consumption. In many cases, determining the geographic origin becomes a very important part of the investigation. Therefore, it is important to develop more sensitive methods for the analysis of alcoholic beverages. In this review, an attempt has been made to summarize the work accomplished so far in the field of analysis and detection of alcoholic beverages. In this review, various sample preparation techniques for GC-MS analysis of alcoholic beverages have been discussed along with its applications. GC-MS based analysis is less time consuming, more sensitive and more accurate.   Keywords: Forensic Sciences, Alcoholic beverages, Mortality, Analysis, GC-MS

SPME-GC-MS analysis of commercial henna samples (Lawsonia inermis L.).

Science.gov (United States)

Mengoni, Tamara; Peregrina, Dolores Vargas; Censi, Roberta; Cortese, Manuela; Ricciutelli, Massimo; Maggi, Filippo; Di Martino, Piera

2016-01-01

The aim of this work was to provide a characterisation of volatile constituents from different commercial batches of henna (Lawsonia inermis) leaves of different geographic origin. Headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS) was used for the purpose. A total of 72 components were identified by GC-MS in the headspace of different henna samples which proved to differ considerably from each other, because they were characterised by different classes of components, mainly aliphatic compounds (9.0-64.7%), terpenoids (5.8-45.5%) and aromatics (7.9-45.2%), with alkanes (0.9-18.5%), aldehydes (2.1-18.8%) and carboxylic acids (3.1-29.3%), monoterpenes (3.4-30.0%) and sesquiterpenes (0.8-23.7%) and phenyl propanoids (0.6-43.1%), being the most abundant, respectively. Major representatives of these groups were n-hexadecane (0.5-4.7%), (2E)-hexenal (0.5-11.7%) and acetic acid (2.8-24.5%), limonene (0.8-14.7%), carvol (3.8-7.1%), geranyl acetone (1.4-7.9%) and (E)-caryophyllene (3.3-8.4%), and (E)-anethole (0.6-35.0%), respectively. We assume that factors such as the manufacturing process, the storage conditions and the different geographic origin of the samples may contribute to such variability.

Comparison of GC/MSD and GC/AED for the determination of organotin compounds in the environment

Energy Technology Data Exchange (ETDEWEB)

Staeb, J.A. (Inst. of Environmental Studies, Free Univ., Amsterdam (Netherlands)); Cofino, W.P. (Inst. of Environmental Studies, Free Univ., Amsterdam (Netherlands)); Hattum, B. van (Inst. of Environmental Studies, Free Univ., Amsterdam (Netherlands)); Brinkman, U.A.T. (Dept. of Analytical Chemistry, Free Univ., Amsterdam (Netherlands))

Methods are described for the analysis of environmental samples like water, sediment and suspended matter for the determination of all organotin compounds (OTs) that are currently used as biocides: Tributyltin (TBT) triphenyltin (TPT), tricyclohexyltin (TCT) and fenbutatin oxide (FBTO). In water also five degradation products (di and mono substituted analogs) can be determined. Alkylation using a Grignard reagent was used to obtain OT derivatives amenable to gas chromatography (GC). Both methylation and pentylation have been employed for derivatization prior to GC analysis. The present results show that derivatization efficiencies for TPT, TCT and FBTO at trace levels are higher using methylation than pentylation. Detection limits for each type of sample matrix were determined using GC/Mass Selective Detection (GC/MSD) and GC/Atomic Emission Detection (AED). In sediment and suspended matter only tri-substituted OTs (i.e. the parent compounds) could be determined. Detection limits ranged from 0.2 to 10 ng/g dry weight. FBTO, not previously detected in environmental samples, was found at levels of 4 and 11 ng/g in a suspended matter sample and a sediment sample, respectively. In water the OTs and their degradation products were determined at levels of 1-10 ng/l (as tin) using 200 ml water samples. (orig.)

Are the Wild and Laboratory Insect Populations Different in Semiochemical Emission? The Case of the Medfly Sex Pheromone

Czech Academy of Sciences Publication Activity Database

Vaníčková, Lucie; do Nascimento, R. R.; Hoskovec, Michal; Ježková, Z.; Břízová, Radka; Tomčala, Aleš; Kalinová, Blanka

2012-01-01

Roč. 60, č. 29 (2012), s. 7168-7176 ISSN 0021-8561 Institutional support: RVO:61388963 Keywords : GC X GC/TOFMS * GC-EAD * principal component analysis Subject RIV: CC - Organic Chemistry Impact factor: 2.906, year: 2012

Identification and field and laboratory tests of the sex pheromone of Cerconota anonella Sepp. (Lepidoptera: Oecophoridae)

Czech Academy of Sciences Publication Activity Database

Pires, E. V.; Mendonca, A. L.; Vaníčková, Lucie; Serra, M. S. J.; da Silva, R. C. C.; dos Santos, D. C.; Campos, R. S.; Santana, A. E. G.; do Nascimento, R. R.

2016-01-01

Roč. 140, 1/2 (2016), s. 72-80 ISSN 0931-2048 Institutional support: RVO:61388963 Keywords : Annona fruit borer * GC x GC-TOFMS * GC-EAD * sex pheromone Subject RIV: EG - Zoology Impact factor: 1.641, year: 2016

Volatiles from spruce trap-trees detected by Ips typographus bark beetles: chemical and electrophysiological analyses

Czech Academy of Sciences Publication Activity Database

Kalinová, Blanka; Břízová, Radka; Knížek, M.; Turčáni, M.; Hoskovec, Michal

2014-01-01

Roč. 8, č. 4 (2014), s. 305-316 ISSN 1872-8855 Institutional support: RVO:61388963 Keywords : Ips typographus * Picea abies * host selection * semiochemicals * GC-EAD * GC9GC/TOFMS Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 1.462, year: 2014

Flow injection electrochemical hydride generation inductively coupled plasma time-of-flight mass spectrometry for the simultaneous determination of hydride forming elements and its application to the analysis of fresh water samples

International Nuclear Information System (INIS)

Bings, Nicolas H.; Stefanka, Zsolt; Mallada, Sergio Rodriguez

2003-01-01

A flow injection (FI) method was developed using electrochemical hydride generation (EcHG) as a sample introduction system, coupled to an inductively coupled plasma time-of-flight mass spectrometer (ICP-TOFMS) for rapid and simultaneous determination of six elements forming hydrides (As, Bi, Ge, Hg, Sb and Se). A novel low volume electrolysis cell, especially suited for FI experiments was designed and the conditions for simultaneous electrochemical hydride generation (EcHG; electrolyte concentrations and flow rates, electrolysis voltage and current) as well as the ICP-TOFMS operational parameters (carrier gas flow rate, modulation pulse width (MPW)) for the simultaneous determination of 12 isotopes were optimized. The compromise operation parameters of the electrolysis were found to be 1.4 and 3 ml min -1 for the anolyte and catholyte flow rates, respectively, using 2 M sulphuric acid. An optimum electrolysis current of 0.7 A (16 V) and an argon carrier gas flow rate of 0.91 l min -1 were chosen. A modulation pulse width of 5 μs, which influences the sensitivity through the amount of ions being collected by the MS per single analytical cycle, provided optimum results for the detection of transient signals. The achieved detection limits were compared with those obtained by using FI in combination with conventional nebulization (FI-ICP-TOFMS); values for chemical hydride generation (FI-CHG-ICP-TOFMS) were taken from the literature. By using a 200 μl sample loop absolute detection limits (3σ) in the range of 10-160 pg for As, Bi, Ge, Hg, Sb and 1.1 ng for Se and a precision of 4-8% for seven replicate injections of 20-100 ng ml -1 multielemental sample solutions were achieved. The analysis of a standard reference material (SRM) 1643d (NIST, 'Trace Elements in Water') showed good agreement with the certified values for As and Sb. Se showed a drastic difference, which is probably due to the presence of hydride-inactive Se species in the sample. Recoveries better than

Improved determination of flavour compounds in butter by solid-phase (micro)extraction and comprehensive two-dimensional gas chromatography

NARCIS (Netherlands)

Adahchour, M.; Wiewel, J.; Verdel, R.; Vreuls, R.J.J.; Brinkman, U.A.T.

2005-01-01

The practicability and potential of comprehensive two-dimensional gas chromatography (GC × GC) coupled to both conventional flame ionisation (FID) and time-of-flight mass spectrometric (TOF-MS) detection, were compared with those of conventional one-dimensional (1D) GC, with the determination of

GC and GC-MS characterization of crude oil transformation in sediments and microbial mat samples after the 1991 oil spill in the Saudi Arabian Gulf coast

International Nuclear Information System (INIS)

Garcia de Oteyza, T.; Grimalt, J.O.

2006-01-01

The massive oil discharge in the Saudi Arabian coast at the end of the 1991 Gulf War is used here as a natural experiment to study the ability of microbial mats to transform oil residues after major spills. The degree of oil transformation has been evaluated from the analysis of the aliphatic and aromatic hydrocarbons by gas chromatography (GC) and GC coupled to mass spectrometry (GC-MS). The oil-polluted microbial mat samples from coastal environments exhibited an intermediate degree of transformation between that observed in superficial and deep sediments. Evaporation, photo-oxidation and water-washing seemed to lead to more effective and rapid elimination of hydrocarbons than cyanobacteria and its associated microorganisms. Furthermore, comparison of some compounds (e.g. regular isoprenoid hydrocarbons or alkylnaphthalenes) in the oil collected in the area after the spill or in the mixtures retained by cyanobacterial growth gave rise to an apparent effect of hydrocarbon preservation in the microbial mat ecosystems. - Cyanobacterial mats inhibit degradation of oil by reducing exposure to the atmosphere and seawater

Gc protein (vitamin D-binding protein): Gc genotyping and GcMAF precursor activity.

Science.gov (United States)

Nagasawa, Hideko; Uto, Yoshihiro; Sasaki, Hideyuki; Okamura, Natsuko; Murakami, Aya; Kubo, Shinichi; Kirk, Kenneth L; Hori, Hitoshi

2005-01-01

The Gc protein (human group-specific component (Gc), a vitamin D-binding protein or Gc globulin), has important physiological functions that include involvement in vitamin D transport and storage, scavenging of extracellular G-actin, enhancement of the chemotactic activity of C5a for neutrophils in inflammation and macrophage activation (mediated by a GalNAc-modified Gc protein (GcMAF)). In this review, the structure and function of the Gc protein is focused on especially with regard to Gc genotyping and GcMAF precursor activity. A discussion of the research strategy "GcMAF as a target for drug discovery" is included, based on our own research.

An automated GC-C-GC-IRMS setup to measure palaeoatmospheric δ13C-CH4, δ15N-N2O and δ18O-N2O in one ice core sample

Directory of Open Access Journals (Sweden)

P. Sperlich

2013-08-01

Full Text Available Air bubbles in ice core samples represent the only opportunity to study the mixing ratio and isotopic variability of palaeoatmospheric CH4 and N2O. The highest possible precision in isotope measurements is required to maximize the resolving power for CH4 and N2O sink and source reconstructions. We present a new setup to measure δ13C-CH4, δ15N-N2O and δ18O-N2O isotope ratios in one ice core sample and with one single IRMS instrument, with a precision of 0.09, 0.6 and 0.7‰, respectively, as determined on 0.6–1.6 nmol CH4 and 0.25–0.6 nmol N2O. The isotope ratios are referenced to the VPDB scale (δ13C-CH4, the N2-air scale (δ15N-N2O and the VSMOW scale (δ18O-N2O. Ice core samples of 200–500 g are melted while the air is constantly extracted to minimize gas dissolution. A helium carrier gas flow transports the sample through the analytical system. We introduce a new gold catalyst to oxidize CO to CO2 in the air sample. CH4 and N2O are then separated from N2, O2, Ar and CO2 before they get pre-concentrated and separated by gas chromatography. A combustion unit is required for δ13C-CH4 analysis, which is equipped with a constant oxygen supply as well as a post-combustion trap and a post-combustion GC column (GC-C-GC-IRMS. The post-combustion trap and the second GC column in the GC-C-GC-IRMS combination prevent Kr and N2O interferences during the isotopic analysis of CH4-derived CO2. These steps increase the time for δ13C-CH4 measurements, which is used to measure δ15N-N2O and δ18O-N2O first and then δ13C-CH4. The analytical time is adjusted to ensure stable conditions in the ion source before each sample gas enters the IRMS, thereby improving the precision achieved for measurements of CH4 and N2O on the same IRMS. The precision of our measurements is comparable to or better than that of recently published systems. Our setup is calibrated by analysing multiple reference gases that were injected over bubble-free ice samples. We show

Radioimmunoassay screening and GC/MS confirmation of whole blood samples for drugs of abuse

Energy Technology Data Exchange (ETDEWEB)

Spiehler, V.R.; Sedgwick, P.

From 1981 to 1984, an average of 300 radioimmunoassay screens on whole blood were performed each week in the authors laboratory. Most samples were screened for opiates phencyclidine and its analogs, barbiturates, and cocaine or its metabolite benzoylecgonine. A commercially available radioimmunoassay was used with modifications to facilitate screening of whole blood. Increasing sample size increased the sensitivity of the assay. Changing reagent concentration (1:1 dilution), incubation time, sample matrix (water, urine, or blood), or fraction counted (precipitate or supernatant) did not affect the utility of the standard curve or the sensitivity of the assay. All positive results for phencyclidine, opiates, cocaine, and related compounds were confirmed by GC/MA. Barbiturate positives were confirmed by UV spectrophotometry.

Identification of two components of the female sex pheromone of the sugarcane-borer Diatraea flavipennella (Lepidoptera: Crambidae)

Czech Academy of Sciences Publication Activity Database

Kalinová, Blanka; do Nascimento, R. R.; Hoskovec, Michal; Mendonca, A. L.; Silva, E. L.; De Freitas, M. R. T.; Cabral Jr, C. R.; Silva, C. E.; Santana, A. E. G.; Svatoš, Aleš

2012-01-01

Roč. 136, č. 3 (2012), s. 203-211 ISSN 0931-2048 Institutional research plan: CEZ:AV0Z40550506 Keywords : Diatraea flavipennella * sex pheromone * GCxGC-TOFMS * GC-EAD Subject RIV: CC - Organic Chemistry Impact factor: 1.560, year: 2012

Bio-oil production of softwood and hardwood forest industry residues through fast and intermediate pyrolysis and its chromatographic characterization.

Science.gov (United States)

Torri, Isadora Dalla Vecchia; Paasikallio, Ville; Faccini, Candice Schmitt; Huff, Rafael; Caramão, Elina Bastos; Sacon, Vera; Oasmaa, Anja; Zini, Claudia Alcaraz

2016-01-01

Bio-oils were produced through intermediate (IP) and fast pyrolysis (FP), using Eucalyptus sp. (hardwood) and Picea abies (softwood), wood wastes produced in large scale in Pulp and Paper industries. Characterization of these bio-oils was made using GC/qMS and GC×GC/TOFMS. The use of GC×GC provided a broader characterization of bio-oils and it allowed tracing potential markers of hardwood bio-oil, such as dimethoxy-phenols, which might co-elute in 1D-GC. Catalytic FP increased the percentage of aromatic hydrocarbons in P. abies bio-oil, indicating its potential for fuel production. However, the presence of polyaromatic hydrocarbons (PAH) draws attention to the need of a proper management of pyrolysis process in order to avoid the production of toxic compounds and also to the importance of GC×GC/TOFMS use to avoid co-elutions and consequent inaccuracies related to identification and quantification associated with GC/qMS. Ketones and phenols were the major bio-oil compounds and they might be applied to polymer production. Copyright © 2015 Elsevier Ltd. All rights reserved.

Infrared biospectroscopy for a fast qualitative evaluation of sample preparation in metabolomics.

Science.gov (United States)

Kuligowski, Julia; Pérez-Guaita, David; Escobar, Javier; Lliso, Isabel; de la Guardia, Miguel; Lendl, Bernhard; Vento, Máximo; Quintás, Guillermo

2014-09-01

Liquid chromatography-mass spectrometry (LC-MS) has been increasingly used in biomedicine to study the dynamic metabolomic responses of biological systems under different physiological or pathological conditions. To obtain an integrated snapshot of the system, metabolomic methods in biomedicine typically analyze biofluids (e.g. plasma) that require clean-up before being injected into LC-MS systems. However, high resolution LC-MS is costly in terms of resources required for sample and data analysis and care must be taken to prevent chemical (e.g. ion suppression) or statistical artifacts. Because of that, the effect of sample preparation on the metabolomic profile during metabolomic method development is often overlooked. This work combines an Attenuated Total Reflectance-Fourier transform infrared (ATR-FTIR) and a multivariate exploratory data analysis for a cost-effective qualitative evaluation of major changes in sample composition during sample preparation. ATR-FTIR and LC-time of flight mass spectrometry (TOFMS) data from the analysis of a set of plasma samples precipitated using acetonitrile, methanol and acetone performed in parallel were used as a model example. Biochemical information obtained from the analysis of the ATR-FTIR and LC-TOFMS data was thoroughly compared to evaluate the strengths and shortcomings of FTIR biospectroscopy for assessing sample preparation in metabolomics studies. Results obtained show the feasibility of ATR-FTIR for the evaluation of major trends in the plasma composition changes among different sample pretreatments, providing information in terms of e.g., amino acids, proteins, lipids and carbohydrates overall contents comparable to those found by LC-TOFMS. Copyright © 2014 Elsevier B.V. All rights reserved.

Mass spectrometry of solid samples in open air using combined laser ionization and ambient metastable ionization

International Nuclear Information System (INIS)

He, X.N.; Xie, Z.Q.; Gao, Y.; Hu, W.; Guo, L.B.; Jiang, L.; Lu, Y.F.

2012-01-01

Mass spectrometry of solid samples in open air was carried out using combined laser ionization and metastable ionization time-of-flight mass spectrometry (LI-MI-TOFMS) in ambient environment for qualitative and semiquantitative (relative analyte information, not absolute information) analysis. Ambient metastable ionization using a direct analysis in realtime (DART) ion source was combined with laser ionization time-of-flight mass spectrometry (LI-TOFMS) to study the effects of combining metastable and laser ionization. A series of metallic samples from the National Institute of Standards and Technology (NIST 494, 495, 498, 499, and 500) and a pure carbon target were characterized using LI-TOFMS in open air. LI-MI-TOFMS was found to be superior to laser-induced breakdown spectroscopy (LIBS). Laser pulse energies between 10 and 200 mJ at the second harmonic (532 nm) of an Nd:YAG laser were applied in the experiment to obtain a high degree of ionization in plasmas. Higher laser pulse energy improves signal intensities of trace elements (such as Fe, Cr, Mn, Ni, Ca, Al, and Ag). Data were analyzed by numerically calculating relative sensitivity coefficients (RSCs) and limit of detections (LODs) from mass spectrometry (MS) and LIBS spectra. Different parameters, such as boiling point, ionization potential, RSC, LOD, and atomic weight, were shown to analyze the ionization and MS detection processes in open air.

Characterization of olive oil volatiles by multi-step direct thermal desorption-comprehensive gas chromatography-time-of-flight mass spectrometry using a programmed temperature vaporizing injector

NARCIS (Netherlands)

de Koning, S.; Kaal, E.; Janssen, H.-G.; van Platerink, C.; Brinkman, U.A.Th.

2008-01-01

The feasibility of a versatile system for multi-step direct thermal desorption (DTD) coupled to comprehensive gas chromatography (GC × GC) with time-of-flight mass spectrometric (TOF-MS) detection is studied. As an application the system is used for the characterization of fresh versus aged olive

Analyses of volatiles produced by the African fruit fly species complex (Diptera, Tephritidae)

Czech Academy of Sciences Publication Activity Database

Břízová, Radka; Vaníčková, Lucie; Faťarová, M.; Ekesi, S.; Hoskovec, Michal; Kalinová, Blanka

-, č. 540 (2015), s. 385-404 ISSN 1313-2989 Institutional support: RVO:61388963 Keywords : Ceratitis FAR complex * chemotaxonomy * male and female-borne volatiles * GCxGC-TOFMS * GC-EAD Subject RIV: EG - Zoology Impact factor: 0.938, year: 2015 http://zookeys.pensoft.net/articles.php?id=6223

Comparison of Spot and Time Weighted Averaging (TWA Sampling with SPME-GC/MS Methods for Trihalomethane (THM Analysis

Directory of Open Access Journals (Sweden)

Don-Roger Parkinson

2016-02-01

Full Text Available Water samples were collected and analyzed for conductivity, pH, temperature and trihalomethanes (THMs during the fall of 2014 at two monitored municipal drinking water source ponds. Both spot (or grab and time weighted average (TWA sampling methods were assessed over the same two day sampling time period. For spot sampling, replicate samples were taken at each site and analyzed within 12 h of sampling by both Headspace (HS- and direct (DI- solid phase microextraction (SPME sampling/extraction methods followed by Gas Chromatography/Mass Spectrometry (GC/MS. For TWA, a two day passive on-site TWA sampling was carried out at the same sampling points in the ponds. All SPME sampling methods undertaken used a 65-µm PDMS/DVB SPME fiber, which was found optimal for THM sampling. Sampling conditions were optimized in the laboratory using calibration standards of chloroform, bromoform, bromodichloromethane, dibromochloromethane, 1,2-dibromoethane and 1,2-dichloroethane, prepared in aqueous solutions from analytical grade samples. Calibration curves for all methods with R2 values ranging from 0.985–0.998 (N = 5 over the quantitation linear range of 3–800 ppb were achieved. The different sampling methods were compared for quantification of the water samples, and results showed that DI- and TWA- sampling methods gave better data and analytical metrics. Addition of 10% wt./vol. of (NH42SO4 salt to the sampling vial was found to aid extraction of THMs by increasing GC peaks areas by about 10%, which resulted in lower detection limits for all techniques studied. However, for on-site TWA analysis of THMs in natural waters, the calibration standard(s ionic strength conditions, must be carefully matched to natural water conditions to properly quantitate THM concentrations. The data obtained from the TWA method may better reflect actual natural water conditions.

Quantification of compositional changes of petroleum hydrocarbons by GC/FID and GC/MS during a long-term bioremediation experiment

DEFF Research Database (Denmark)

Jensen, Trine S.; Arvin, Erik; Svensmark, Bo

2000-01-01

Samples from a long-term bioremediation experiment contaminated with two crude oils, Arabian Heavy and Gullfax, was used to analyze the compositional change of petroleum hydrocarbons. A time course of five different homologous series of petroleum hydrocarbons were analysed by GC/FID and GC...

Approaches of aroma extraction dilution analysis (AEDA) for headspace solid phase microextraction and gas chromatography-olfactometry (HS-SPME-GC-O): Altering sample amount, diluting the sample or adjusting split ratio?

Science.gov (United States)

Feng, Yunzi; Cai, Yu; Sun-Waterhouse, Dongxiao; Cui, Chun; Su, Guowan; Lin, Lianzhu; Zhao, Mouming

2015-11-15

Aroma extract dilution analysis (AEDA) is widely used for the screening of aroma-active compounds in gas chromatography-olfactometry (GC-O). In this study, three aroma dilution methods, (I) using different test sample volumes, (II) diluting samples, and (III) adjusting the GC injector split ratio, were compared for the analysis of volatiles by using HS-SPME-AEDA. Results showed that adjusting the GC injector split ratio (III) was the most desirable approach, based on the linearity relationships between Ln (normalised peak area) and Ln (normalised flavour dilution factors). Thereafter this dilution method was applied in the analysis of aroma-active compounds in Japanese soy sauce and 36 key odorants were found in this study. The most intense aroma-active components in Japanese soy sauce were: ethyl 2-methylpropanoate, ethyl 2-methylbutanoate, ethyl 3-methylbutanoate, ethyl 4-methylpentanoate, 3-(methylthio)propanal, 1-octen-3-ol, 2-methoxyphenol, 4-ethyl-2-methoxyphenol, 2-methoxy-4-vinylphenol, 2-phenylethanol, and 4-hydroxy-5-ethyl-2-methyl-3(2H)-furanone. Copyright © 2015. Published by Elsevier Ltd.

Group separation of organohalogenated contaminants by GCxGC

Energy Technology Data Exchange (ETDEWEB)

Korytar, P.; Leonards, P.; Boer, J. de [Netherlands Institute for Fisheries Research, IJmuiden (Netherlands); Parera, J. [Barcelona Univ. (Spain); Brinkman, U. [Vrije Univ., Amsterdam (Netherlands)

2004-09-15

The congener specific analysis of organohalogenated compounds is challenging, because of a large number of possibly interfering compounds not only within the compound class but also from congeners of other compound classes. Therefore, analytical procedures usually include complicated and time-consuming multi-step sample pre-treatment and/or selective detection (e.g. HRMS, MS/MS) in the consequent gas chromatographic analysis, what makes the procedures laborious and expensive. One way how to improve the situation would be to considerably increase the separation efficiency of the gas chromatographic analysis by replacing conventional GC by so-called comprehensive two-dimensional gas chromatography (GC x GC). In GC x GC two independent separations are applied to an entire sample which effects a considerably enhanced overall resolution and also, because of the analyte refocusing during modulation, an improved analyte detectability. One further aspect which makes GC x GC especially attractive is the ordered structure of the two-dimensional chromatograms, which is observed when mixtures of related compounds, homologues or congeners are analysed. One good example are the bands of alkanes, naphthenes and aromatics present in 2D chromatogram when petrochemical samples are analysed. The ordered structure was reported also within the compound class of some organohalogenated contaminants, more precisely, of polychlorinated biphenyls and toxaphenes (ordering to number of chlorine atoms on the skeleton). However, to date, no study of separation among the different compound classes has been reported. In the present paper, this topic will be studied for the most common contaminants. While the principle aim is the group type separation, some attention will be devoted also to within the class separation (e.g., for polychlorinated diphenylethers and polychlorinated alkanes).

Characterisation of middle-distillates by comprehensive two-dimensional gas chromatography (GC x GC): A powerful alternative for performing various standard analysis of middle-distillates.

Science.gov (United States)

Vendeuvre, Colombe; Ruiz-Guerrero, Rosario; Bertoncini, Fabrice; Duval, Laurent; Thiébaut, Didier; Hennion, Marie-Claire

2005-09-09

The detailed characterisation of middle distillates is essential for a better understanding of reactions involved in refining process. Owing to higher resolution power and enhanced sensitivity, comprehensive two-dimensional gas chromatography (GC x GC) is a powerful tool for improving characterisation of petroleum samples. The aim of this paper is to compare GC x GC and various ASTM methods -- gas chromatography (GC), liquid chromatography (LC) and mass spectrometry (MS) -- for group type separation and detailed hydrocarbon analysis. Best features of GC x GC are demonstrated and compared to these techniques in terms of cost, time consumption and accuracy. In particular, a new approach of simulated distillation (SimDis-GC x GC) is proposed: compared to the standard method ASTM D2887 it gives unequal information for better understanding of conversion process.

Analysis of Alkaloids from Physalis peruviana by Capillary GC, Capillary GC-MS, and GC-FTIR.

Science.gov (United States)

Kubwabo, C; Rollmann, B; Tilquin, B

1993-04-01

The alkaloid composition of the aerial parts and roots of PHYSALIS PERUVIANA was analysed by capillary GC (GC (2)), GC (2)-MS and GC (2)-FTIR. Eight alkaloids were identified, three of those alkaloids are 3beta-acetoxytropane and two N-methylpyrrolidinylhygrine isomers, which were not previously found in the genus PHYSALIS. A reproduction of the identification of alkaloids detected in the plant by the use of retention indices has been proposed.

Determination of Porosity in Shale by Double Headspace Extraction GC Analysis.

Science.gov (United States)

Zhang, Chun-Yun; Li, Teng-Fei; Chai, Xin-Sheng; Xiao, Xian-Ming; Barnes, Donald

2015-11-03

This paper reports on a novel method for the rapid determination of the shale porosity by double headspace extraction gas chromatography (DHE-GC). Ground core samples of shale were placed into headspace vials and DHE-GC measurements of released methane gas were performed at a given time interval. A linear correlation between shale porosity and the ratio of consecutive GC signals was established both theoretically and experimentally by comparing with the results from the standard helium pycnometry method. The results showed that (a) the porosity of ground core samples of shale can be measured within 30 min; (b) the new method is not significantly affected by particle size of the sample; (c) the uncertainties of measured porosities of nine shale samples by the present method range from 0.31 to 0.46 p.u.; and (d) the results obtained by the DHE-GC method are in a good agreement with those from the standard helium pycnometry method. In short, the new DHE-GC method is simple, rapid, and accurate, making it a valuable tool for shale gas-related research and applications.

Screening of oil sources by using comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry and multivariate statistical analysis.

Science.gov (United States)

Zhang, Wanfeng; Zhu, Shukui; He, Sheng; Wang, Yanxin

2015-02-06

Using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/TOFMS), volatile and semi-volatile organic compounds in crude oil samples from different reservoirs or regions were analyzed for the development of a molecular fingerprint database. Based on the GC×GC/TOFMS fingerprints of crude oils, principal component analysis (PCA) and cluster analysis were used to distinguish the oil sources and find biomarkers. As a supervised technique, the geological characteristics of crude oils, including thermal maturity, sedimentary environment etc., are assigned to the principal components. The results show that tri-aromatic steroid (TAS) series are the suitable marker compounds in crude oils for the oil screening, and the relative abundances of individual TAS compounds have excellent correlation with oil sources. In order to correct the effects of some other external factors except oil sources, the variables were defined as the content ratio of some target compounds and 13 parameters were proposed for the screening of oil sources. With the developed model, the crude oils were easily discriminated, and the result is in good agreement with the practical geological setting. Copyright © 2014 Elsevier B.V. All rights reserved.

Sample introduction systems for the analysis of liquid microsamples by ICP-AES and ICP-MS

Energy Technology Data Exchange (ETDEWEB)

Todoli, Jose L. [Departamento de Quimica Analitica, Nutricion y Bromatologia, Universidad de Alicante, 03080 Alicante (Spain)]. E-mail: jose.todoli@ua.es; Mermet, Jean M. [Spectroscopy Forever, 01390 Tramoyes (France)

2006-03-15

There are many fields in which the available sample volume is the limiting factor for an elemental analysis. Over the last ten years, sample introduction systems used in plasma spectrometry (i.e., Inductively Coupled Plasma Atomic Emission Spectrometry, ICP-AES, and Mass Spectrometry, ICP-MS) have evolved in order to expand the field of applicability of these techniques to the analysis of micro- and nanosamples. A full understanding of the basic processes occurring throughout the sample introduction system is absolutely necessary to improve analytical performance. The first part of the present review deals with fundamental studies concerning the different phenomena taking place from aerosol production to analyte excitation/ionization when the liquid consumption rate does not exceed 100 {mu}l/min. Existing sample introduction systems are currently far from the ideal and a significant effort has been made to develop new and efficient devices. Different approaches for continuously introducing small sample volumes (i.e., microsamples) have been reviewed and compared in the present work. Finally, applications as well as basic guidelines to select the best sample introduction system according to the sample particularities are given at the end of this review.

Sample introduction systems for the analysis of liquid microsamples by ICP-AES and ICP-MS

International Nuclear Information System (INIS)

Todoli, Jose L.; Mermet, Jean M.

2006-01-01

There are many fields in which the available sample volume is the limiting factor for an elemental analysis. Over the last ten years, sample introduction systems used in plasma spectrometry (i.e., Inductively Coupled Plasma Atomic Emission Spectrometry, ICP-AES, and Mass Spectrometry, ICP-MS) have evolved in order to expand the field of applicability of these techniques to the analysis of micro- and nanosamples. A full understanding of the basic processes occurring throughout the sample introduction system is absolutely necessary to improve analytical performance. The first part of the present review deals with fundamental studies concerning the different phenomena taking place from aerosol production to analyte excitation/ionization when the liquid consumption rate does not exceed 100 μl/min. Existing sample introduction systems are currently far from the ideal and a significant effort has been made to develop new and efficient devices. Different approaches for continuously introducing small sample volumes (i.e., microsamples) have been reviewed and compared in the present work. Finally, applications as well as basic guidelines to select the best sample introduction system according to the sample particularities are given at the end of this review

Gas chromatography coupled to atmospheric pressure ionization mass spectrometry (GC-API-MS): review.

Science.gov (United States)

Li, Du-Xin; Gan, Lin; Bronja, Amela; Schmitz, Oliver J

2015-09-03

Although the coupling of GC/MS with atmospheric pressure ionization (API) has been reported in 1970s, the interest in coupling GC with atmospheric pressure ion source was expanded in the last decade. The demand of a "soft" ion source for preserving highly diagnostic molecular ion is desirable, as compared to the "hard" ionization technique such as electron ionization (EI) in traditional GC/MS, which fragments the molecule in an extensive way. These API sources include atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), atmospheric pressure laser ionization (APLI), electrospray ionization (ESI) and low temperature plasma (LTP). This review discusses the advantages and drawbacks of this analytical platform. After an introduction in atmospheric pressure ionization the review gives an overview about the history and explains the mechanisms of various atmospheric pressure ionization techniques used in combination with GC such as APCI, APPI, APLI, ESI and LTP. Also new developments made in ion source geometry, ion source miniaturization and multipurpose ion source constructions are discussed and a comparison between GC-FID, GC-EI-MS and GC-API-MS shows the advantages and drawbacks of these techniques. The review ends with an overview of applications realized with GC-API-MS. Copyright © 2015. Published by Elsevier B.V.

Compound-specific nitrogen and carbon isotope analysis of nitroaromatic compounds in aqueous samples using solid-phase microextraction coupled to GC/IRMS.

Science.gov (United States)

Berg, Michael; Bolotin, Jakov; Hofstetter, Thomas B

2007-03-15

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry was used to determine the delta15N and delta13C signatures of selected nitroaromatic contaminants such as the explosive 2,4,6-trinitrotoluene (TNT) for derivation of isotopic enrichment factors of contaminant transformation. Parameters for efficient extraction of nitroaromatic compounds (NACs) and substituted anilines from water samples were evaluated by SPME-GC/MS. delta13C signatures determined by SPME-GC/IRMS and elemental analyzer IRMS (EA-IRMS) were in good agreement, generally within +/-0.7 per thousand, except for 2,4-dinitrotoluene (2,4-DNT) and TNT, which showed slight deviations (IRMS were between 73 and 780 microg L-1 and correlated with the extraction efficiencies of the compounds determined by SPME-GC/MS. Nitrogen isotope measurements by SPME-GC/IRMS were of similar precision (standard deviations IRMS within +/-1.3 per thousand (+2.5 per thousand for TNT), but no systematic trend was found for the deviations. LODs of delta15N measurements ranged from 1.6 to 9.6 mg L-1 for nitrotoluenes, chlorinated NACs and DNTs (22 mg L-1 for TNT). The SPME-GC/IRMS method is well suited for the determination of isotopic enrichment factors of various NAC transformation processes and provides so far unexplored possibilities to elucidate behavior and degradation mechanisms of nitroaromatic contaminants in soils and groundwaters.

Quality Control Of Selected Pesticides With GC

Energy Technology Data Exchange (ETDEWEB)

Karasali, H. [Benaki Phytopathological Institute Laboratory of Physical and Chemical Analysis of Pesticides, Ekalis (Greece)

2009-07-15

The practical quality control of selected pesticides with GC is treated. Detailed descriptions are given on materials and methods used, including sample preparation and GC operating conditions. The systematic validation of multi methods is described, comprising performance characteristics in routine analysis, like selectivity, specificity etc. This is illustrated by chromatograms, calibration curves and tables derived from real laboratory data. (author)

Analysis of plant gums and saccharide materials in paint samples: comparison of GC-MS analytical procedures and databases.

Science.gov (United States)

Lluveras-Tenorio, Anna; Mazurek, Joy; Restivo, Annalaura; Colombini, Maria Perla; Bonaduce, Ilaria

2012-10-10

Saccharide materials have been used for centuries as binding media, to paint, write and illuminate manuscripts and to apply metallic leaf decorations. Although the technical literature often reports on the use of plant gums as binders, actually several other saccharide materials can be encountered in paint samples, not only as major binders, but also as additives. In the literature, there are a variety of analytical procedures that utilize GC-MS to characterize saccharide materials in paint samples, however the chromatographic profiles are often extremely different and it is impossible to compare them and reliably identify the paint binder. This paper presents a comparison between two different analytical procedures based on GC-MS for the analysis of saccharide materials in works-of-art. The research presented here evaluates the influence of the analytical procedure used, and how it impacts the sugar profiles obtained from the analysis of paint samples that contain saccharide materials. The procedures have been developed, optimised and systematically used to characterise plant gums at the Getty Conservation Institute in Los Angeles, USA (GCI) and the Department of Chemistry and Industrial Chemistry of the University of Pisa, Italy (DCCI). The main steps of the analytical procedures and their optimisation are discussed. The results presented highlight that the two methods give comparable sugar profiles, whether the samples analysed are simple raw materials, pigmented and unpigmented paint replicas, or paint samples collected from hundreds of centuries old polychrome art objects. A common database of sugar profiles of reference materials commonly found in paint samples was thus compiled. The database presents data also from those materials that only contain a minor saccharide fraction. This database highlights how many sources of saccharides can be found in a paint sample, representing an important step forward in the problem of identifying polysaccharide binders in

Integration of GC-MSD and ER-Calux® assay into a single protocol for determining steroid estrogens in environmental samples.

Science.gov (United States)

Avberšek, Miha; Žegura, Bojana; Filipič, Metka; Heath, Ester

2011-11-01

There are many published studies that use either chemical or biological methods to investigate steroid estrogens in the aquatic environment, but rarer are those that combine both. In this study, gas chromatography with mass selective detection (GC-MSD) and the ER-Calux(®) estrogenicity assay were integrated into a single protocol for simultaneous determination of natural (estrone--E1, 17β-estradiol--E2, estriol--E3) and synthetic (17α-ethinylestradiol--EE2) steroid estrogens concentrations and the total estrogenic potential of environmental samples. For integration purposes, several solvents were investigated and the commonly used dimethyl sulphoxide (DMSO) in the ER-Calux(®) assay was replaced by ethyl acetate, which is more compatible with gas chromatography and enables the same sample to be analysed by both GC-MSD and the ER-Calux(®) assay. The integrated protocol was initially tested using a standard mixture of estrogens. The results for pure standards showed that the estrogenicity calculated on the basis of GC-MSD and the ER-Calux(®) assay exhibited good correlation (r(2)=0.96; α=0.94). The result remained the same when spiked waste water extracts were tested (r(2)=0.92, α=1.02). When applied to real waste water influent and effluent samples the results proved (r(2)=0.93; α=0.99) the applicability of the protocol. The main advantages of this newly developed protocol are simple sample handling for both methods, and reduced material consumption and labour. In addition, it can be applied as either a complete or sequential analysis where the ER-Calux(®) assay is used as a pre-screening method prior to the chemical analysis. Copyright © 2011 Elsevier B.V. All rights reserved.

Gas chromatography coupled to atmospheric pressure ionization mass spectrometry (GC-API-MS): Review

International Nuclear Information System (INIS)

Li, Du-Xin; Gan, Lin; Bronja, Amela; Schmitz, Oliver J.

2015-01-01

Although the coupling of GC/MS with atmospheric pressure ionization (API) has been reported in 1970s, the interest in coupling GC with atmospheric pressure ion source was expanded in the last decade. The demand of a “soft” ion source for preserving highly diagnostic molecular ion is desirable, as compared to the “hard” ionization technique such as electron ionization (EI) in traditional GC/MS, which fragments the molecule in an extensive way. These API sources include atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), atmospheric pressure laser ionization (APLI), electrospray ionization (ESI) and low temperature plasma (LTP). This review discusses the advantages and drawbacks of this analytical platform. After an introduction in atmospheric pressure ionization the review gives an overview about the history and explains the mechanisms of various atmospheric pressure ionization techniques used in combination with GC such as APCI, APPI, APLI, ESI and LTP. Also new developments made in ion source geometry, ion source miniaturization and multipurpose ion source constructions are discussed and a comparison between GC-FID, GC-EI-MS and GC-API-MS shows the advantages and drawbacks of these techniques. The review ends with an overview of applications realized with GC-API-MS. - Highlights: • Atmospheric pressure ion sources (APCI, ESI, APPI, APLC etc) enable the coupling of LC-based high-end MS to GC. • APIs show advantages in selectivity and sensitivity compared with EI in GC-MS. • Accurate mass database in GC-APCI/MS is emerging as an alternative to GC-EI/MS database.

Gas chromatography coupled to atmospheric pressure ionization mass spectrometry (GC-API-MS): Review

Energy Technology Data Exchange (ETDEWEB)

Li, Du-Xin; Gan, Lin; Bronja, Amela [University of Duisburg-Essen, Applied Analytical Chemistry, Universitaetsstr. 5-7, 45141 Essen (Germany); Schmitz, Oliver J., E-mail: oliver.schmitz@uni-due.de [University of Duisburg-Essen, Applied Analytical Chemistry, Universitaetsstr. 5-7, 45141 Essen (Germany)

2015-09-03

Although the coupling of GC/MS with atmospheric pressure ionization (API) has been reported in 1970s, the interest in coupling GC with atmospheric pressure ion source was expanded in the last decade. The demand of a “soft” ion source for preserving highly diagnostic molecular ion is desirable, as compared to the “hard” ionization technique such as electron ionization (EI) in traditional GC/MS, which fragments the molecule in an extensive way. These API sources include atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), atmospheric pressure laser ionization (APLI), electrospray ionization (ESI) and low temperature plasma (LTP). This review discusses the advantages and drawbacks of this analytical platform. After an introduction in atmospheric pressure ionization the review gives an overview about the history and explains the mechanisms of various atmospheric pressure ionization techniques used in combination with GC such as APCI, APPI, APLI, ESI and LTP. Also new developments made in ion source geometry, ion source miniaturization and multipurpose ion source constructions are discussed and a comparison between GC-FID, GC-EI-MS and GC-API-MS shows the advantages and drawbacks of these techniques. The review ends with an overview of applications realized with GC-API-MS. - Highlights: • Atmospheric pressure ion sources (APCI, ESI, APPI, APLC etc) enable the coupling of LC-based high-end MS to GC. • APIs show advantages in selectivity and sensitivity compared with EI in GC-MS. • Accurate mass database in GC-APCI/MS is emerging as an alternative to GC-EI/MS database.

Development of a split-flow system for high precision variable sample introduction in supercritical fluid chromatography.

Science.gov (United States)

Sakai, Miho; Hayakawa, Yoshihiro; Funada, Yasuhiro; Ando, Takashi; Fukusaki, Eiichiro; Bamba, Takeshi

2017-09-15

In this study, we propose a novel variable sample injection system based on full-loop injection, named the split-flow sample introduction system, for application in supercritical fluid chromatography (SFC). In this system, the mobile phase is split by the differential pressure between two back pressure regulators (BPRs) after full-loop injection suitable for SFC, and this differential pressure determines the introduction rate. Nine compounds with a wide range of characteristics were introduced with high reproducibility and universality, confirming that a robust variable sample injection system was achieved. We also investigated the control factors of our proposed system. Sample introduction was controlled by the ratio between the column-side pressure drops in splitless and split flow, ΔP columnsideinsplitless and ΔP columnsideinsplit , respectively, where ΔP columnsideinsplitless is related to the mobile phase flow rate and composition and the column resistance. When all other conditions are kept constant, increasing the make-up flow induces an additional pressure drop on the column side of the system, which leads to a reduced column-side flow rate, and hence decreased the amount of sample injected, even when the net pressure drop on the column side remains the same. Thus, sample introduction could be highly controlled at low sample introduction rate, regardless of the introduction conditions. This feature is advantageous because, as a control factor, the solvent in the make-up pump is independent of the column-side pressure drop. Copyright © 2017. Published by Elsevier B.V.

Amino acid analysis in physiological samples by GC-MS with propyl chloroformate derivatization and iTRAQ-LC-MS/MS.

Science.gov (United States)

Dettmer, Katja; Stevens, Axel P; Fagerer, Stephan R; Kaspar, Hannelore; Oefner, Peter J

2012-01-01

Two mass spectrometry-based methods for the quantitative analysis of free amino acids are described. The first method uses propyl chloroformate/propanol derivatization and gas chromatography-quadrupole mass spectrometry (GC-qMS) analysis in single-ion monitoring mode. Derivatization is carried out directly in aqueous samples, thereby allowing automation of the entire procedure, including addition of reagents, extraction, and injection into the GC-MS. The method delivers the quantification of 26 amino acids. The isobaric tagging for relative and absolute quantification (iTRAQ) method employs the labeling of amino acids with isobaric iTRAQ tags. The tags contain two different cleavable reporter ions, one for the sample and one for the standard, which are detected by fragmentation in a tandem mass spectrometer. Reversed-phase liquid chromatography of the labeled amino acids is performed prior to mass spectrometric analysis to separate isobaric amino acids. The commercial iTRAQ kit allows for the analysis of 42 physiological amino acids with a respective isotope-labeled standard for each of these 42 amino acids.

Screening for γ-Nonalactone in the Headspace of Freshly Cooked Non-Scented Rice Using SPME/GC-O and SPME/GC-MS

Directory of Open Access Journals (Sweden)

Jie Yu Chen

2009-08-01

Full Text Available The determination of γ-nonalactone as one of the important odor-active compounds in freshly cooked non-scented rice is reported. It was evaluated by gas chromatography-olfactometry (GC-O analysis and identified by gas chromatography-mass spectrometry (GC-MS analysis in the headspace above the freshly cooked non-scented rice samples extracted by using a modified headspace solid-phase microextraction (SPME method. This component had a mass spectrum with a characteristic ion peak at m/z 85 (100% and a linear retention index (RI of 2,023 on a DB Wax column, consistent with those of an authentic sample of γ-nonalactone. The odor characterization of a strong, sweet, coconut-like aroma of this compound was also validated by GC-O comparison with the authentic compound.

Screening for illicit and medicinal drugs in whole blood using fully automated SPE and ultra-high-performance liquid chromatography with TOF-MS with data-independent acquisition.

Science.gov (United States)

Pedersen, Anders Just; Dalsgaard, Petur Weihe; Rode, Andrej Jaroslav; Rasmussen, Brian Schou; Müller, Irene Breum; Johansen, Sys Stybe; Linnet, Kristian

2013-07-01

A broad forensic screening method for 256 analytes in whole blood based on a fully automated SPE robotic extraction and ultra-high-performance liquid chromatography (UHPLC) with TOF-MS with data-independent acquisition has been developed. The limit of identification was evaluated for all 256 compounds and 95 of these compounds were validated with regard to matrix effects, extraction recovery, and process efficiency. The limit of identification ranged from 0.001 to 0.1 mg/kg, and the process efficiency exceeded 50% for 73 of the 95 analytes. As an example of application, 1335 forensic traffic cases were analyzed with the presented screening method. Of these, 992 cases (74%) were positive for one or more traffic-relevant drugs above the Danish legal limits. Commonly abused drugs such as amphetamine, cocaine, and frequent types of benzodiazepines were the major findings. Nineteen less frequently encountered drugs were detected e.g. buprenorphine, butylone, cathine, fentanyl, lysergic acid diethylamide, m-chlorophenylpiperazine, 3,4-methylenedioxypyrovalerone, mephedrone, 4-methylamphetamine, p-fluoroamphetamine, and p-methoxy-N-methylamphetamine. In conclusion, using UHPLC-TOF-MS screening with data-independent acquisition resulted in the detection of common drugs of abuse as well as new designer drugs and more rarely occurring drugs. Thus, TOF-MS screening of blood samples constitutes a practical way for screening traffic cases, with the exception of δ-9-tetrahydrocannabinol, which should be handled in a separate method. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Liquid sample introduction in inductively coupled plasma atomic emission and mass spectrometry — Critical review

International Nuclear Information System (INIS)

Bings, N.H.; Orlandini von Niessen, J.O.; Schaper, J.N.

2014-01-01

Inductively coupled plasma optical emission spectroscopy (ICP-OES) and mass spectrometry (ICP-MS) can be considered as the most important tools in inorganic analytical chemistry. Huge progress has been made since the first analytical applications of the ICP. More stable RF generators, improved spectrometers and detection systems were designed along with the achievements gained from advanced microelectronics, leading to overall greatly improved analytical performance of such instruments. In contrast, for the vast majority of cases liquid sample introduction is still based on the pneumatic principle as described in the late 19th century. High flow pneumatic nebulizers typically demand the use of spray chambers as “aerosol filters” in order to match the prerequisites of an ICP. By this, only a small fraction of the nebulized sample actually contributes to the measured signal. Hence, the development of micronebulizers was brought forward. Those systems produce fine aerosols at low sample uptake rates, but they are even more prone for blocking or clogging than conventional systems in the case of solutions containing a significant amount of total dissolved solids (TDS). Despite the high number of publications devoted to liquid sample introduction, it is still considered the Achilles' heel of atomic spectrometry and it is well accepted, that the technology used for liquid sample introduction is still far from ideal, even when applying state-of-the-art systems. Therefore, this review is devoted to offer an update on developments in the field liquid sample introduction that had been reported until the year 2013. The most recent and noteworthy contributions to this field are discussed, trends are highlighted and future directions are outlined. The first part of this review provides a brief overview on theoretical considerations regarding conventional pneumatic nebulization, the fundamentals on aerosol generation and discusses characteristics of aerosols ideally

Liquid sample introduction in inductively coupled plasma atomic emission and mass spectrometry — Critical review

Energy Technology Data Exchange (ETDEWEB)

Bings, N.H., E-mail: bings@uni-mainz.de; Orlandini von Niessen, J.O.; Schaper, J.N.

2014-10-01

Inductively coupled plasma optical emission spectroscopy (ICP-OES) and mass spectrometry (ICP-MS) can be considered as the most important tools in inorganic analytical chemistry. Huge progress has been made since the first analytical applications of the ICP. More stable RF generators, improved spectrometers and detection systems were designed along with the achievements gained from advanced microelectronics, leading to overall greatly improved analytical performance of such instruments. In contrast, for the vast majority of cases liquid sample introduction is still based on the pneumatic principle as described in the late 19th century. High flow pneumatic nebulizers typically demand the use of spray chambers as “aerosol filters” in order to match the prerequisites of an ICP. By this, only a small fraction of the nebulized sample actually contributes to the measured signal. Hence, the development of micronebulizers was brought forward. Those systems produce fine aerosols at low sample uptake rates, but they are even more prone for blocking or clogging than conventional systems in the case of solutions containing a significant amount of total dissolved solids (TDS). Despite the high number of publications devoted to liquid sample introduction, it is still considered the Achilles' heel of atomic spectrometry and it is well accepted, that the technology used for liquid sample introduction is still far from ideal, even when applying state-of-the-art systems. Therefore, this review is devoted to offer an update on developments in the field liquid sample introduction that had been reported until the year 2013. The most recent and noteworthy contributions to this field are discussed, trends are highlighted and future directions are outlined. The first part of this review provides a brief overview on theoretical considerations regarding conventional pneumatic nebulization, the fundamentals on aerosol generation and discusses characteristics of aerosols ideally

The analysis of dyes in ball point pen inks on single paper fibres using laser desorption ionisation time of flight mass spectrometry (LDI-TOFMS).

Science.gov (United States)

Matthews, Broderick; Walker, G Stewart; Kobus, Hilton; Pigou, Paul; Bird, Carolyne; Smith, Glyn

2011-06-15

An important requisite for the forensic analysis of inks on documents is that damage to the document is avoided or minimised. This paper describes a technique for dye identification in ballpoint pen inks using LDI-TOFMS on single ink bearing paper fibres and its application to a case. A single ink bearing paper fibre can be prised from the surface of the document under a stereo microscope and presented to the instrument for analysis without further treatment. This sampling process causes imperceptible damage to the surface of the document. Clear mass spectrometric identification of the ink dyes is obtained. A case example is provided to illustrate the practical application of the technique. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Gc protein-derived macrophage activating factor (GcMAF): isoelectric focusing pattern and tumoricidal activity.

Science.gov (United States)

Mohamad, Saharuddin Bin; Nagasawa, Hideko; Sasaki, Hideyuki; Uto, Yoshihiro; Nakagawa, Yoshinori; Kawashima, Ken; Hori, Hitoshi

2003-01-01

Gc protein is the precursor for Gc protein-derived macrophage activating factor (GcMAF), with three phenotypes: Gc1f, Gc1s and Gc2, based on its electrophoretic mobility. The difference in electrophoretic mobility is because of the difference in its posttranslational sugar moiety composition. We compared the difference between Gc protein and GcMAF electrophoretic mobility using the isoelectric focusing (IEF) method. The tumoricidal activity of GcMAF-treated macrophage was evaluated after coculture with L-929 cell. The tumoricidal mechanism was investigated using TNF bioassay and nitric oxide (NO) release. The difference in Gc protein and GcMAF electrophoretic mobility was detected. The tumoricidal activity of GcMAF-treated macrophage was detected, but no release of TNF and NO was detected. The difference of isoelectric focusing mobility in Gc protein and GcMAF would be useful to develop a GcMAF detection method. GcMAF increased macrophage tumoricidal activity but TNF and NO release were not involved in the mechanism.

Identification of organic sulfur compounds in coal bitumen obtained by different extraction techniques using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometric detection

Energy Technology Data Exchange (ETDEWEB)

Machado, Maria Elisabete; Cappelli Fontanive, Fernando; Bastos Caramao, Elina; Alcaraz Zini, Claudia [Universidade Federal do Rio Grande do Sul, Instituto de Quimica, Porto Alegre, RS (Brazil); Oliveira, Jose Vladimir de [URI, Universidade Regional Integrada do Alto Uruguai e das Missoes, Erechim, RS (Brazil)

2011-11-15

The determination of organic sulfur compounds (OSC) in coal is of great interest. Technically and operationally these compounds are not easily removed and promote corrosion of equipment. Environmentally, the burning of sulfur compounds leads to the emission of SO{sub x} gases, which are major contributors to acid rain. Health-wise, it is well known that these compounds have mutagenic and carcinogenic properties. Bitumen can be extracted from coal by different techniques, and use of gas chromatography coupled to mass spectrometric detection enables identification of compounds present in coal extracts. The OSC from three different bitumens were tentatively identified by use of three different extraction techniques: accelerated solvent extraction (ASE), ultrasonic extraction (UE), and supercritical-fluid extraction (SFE). Results obtained from one-dimensional gas chromatography (1D GC) coupled to quadrupole mass spectrometric detection (GC-qMS) and from two-dimensional gas chromatography with time-of-flight mass spectrometric detection (GC x GC-TOFMS) were compared. By use of 2D GC, a greater number of OSC were found in ASE bitumen than in SFE and UE bitumens. No OSC were identified with 1D GC-qMS, although some benzothiophenes and dibenzothiophenes were detected by use of EIM and SIM modes. GC x GC-TOFMS applied to investigation of OSC in bitumens resulted in analytical improvement, as more OSC classes and compounds were identified (thiols, sulfides, thiophenes, naphthothiophenes, benzothiophenes, and benzonaphthothiophenes). The roof-tile effect was observed for OSC and PAH in all bitumens. Several co-elutions among analytes and with matrix interferents were solved by use of GC x GC. (orig.)

ADAP-GC 3.0: Improved Peak Detection and Deconvolution of Co-eluting Metabolites from GC/TOF-MS Data for Metabolomics Studies.

Science.gov (United States)

Ni, Yan; Su, Mingming; Qiu, Yunping; Jia, Wei; Du, Xiuxia

2016-09-06

ADAP-GC is an automated computational pipeline for untargeted, GC/MS-based metabolomics studies. It takes raw mass spectrometry data as input and carries out a sequence of data processing steps including construction of extracted ion chromatograms, detection of chromatographic peak features, deconvolution of coeluting compounds, and alignment of compounds across samples. Despite the increased accuracy from the original version to version 2.0 in terms of extracting metabolite information for identification and quantitation, ADAP-GC 2.0 requires appropriate specification of a number of parameters and has difficulty in extracting information on compounds that are in low concentration. To overcome these two limitations, ADAP-GC 3.0 was developed to improve both the robustness and sensitivity of compound detection. In this paper, we report how these goals were achieved and compare ADAP-GC 3.0 against three other software tools including ChromaTOF, AnalyzerPro, and AMDIS that are widely used in the metabolomics community.

ADAP-GC 3.0: Improved Peak Detection and Deconvolution of Co-eluting Metabolites from GC/TOF-MS Data for Metabolomics Studies

Science.gov (United States)

Ni, Yan; Su, Mingming; Qiu, Yunping; Jia, Wei

2017-01-01

ADAP-GC is an automated computational pipeline for untargeted, GC-MS-based metabolomics studies. It takes raw mass spectrometry data as input and carries out a sequence of data processing steps including construction of extracted ion chromatograms, detection of chromatographic peak features, deconvolution of co-eluting compounds, and alignment of compounds across samples. Despite the increased accuracy from the original version to version 2.0 in terms of extracting metabolite information for identification and quantitation, ADAP-GC 2.0 requires appropriate specification of a number of parameters and has difficulty in extracting information of compounds that are in low concentration. To overcome these two limitations, ADAP-GC 3.0 was developed to improve both the robustness and sensitivity of compound detection. In this paper, we report how these goals were achieved and compare ADAP-GC 3.0 against three other software tools including ChromaTOF, AnalyzerPro, and AMDIS that are widely used in the metabolomics community. PMID:27461032

Results of the First Mars Organic Molecule Analyzer (MOMA) GC-MS Coupling

Science.gov (United States)

Buch, Arnaud; Pinnick, Veronica; Szopa, Cyril; Danell, Ryan; Grand, Noel; Van Amerom, Friso; Glavin, Daniel; Freissinet, Caroline; Humeau, Olivier; Coll, Patrice; Arevalo, Ricardo; Stalport, Fabien; Brinckerhoff, William; Steininger, Harald; Goesmann, Fred; Mahaffy, Paul; Raulin, Francois

2014-11-01

The Mars Organic Molecule Analyzer (MOMA) aboard the ExoMars rover will be a key analytical tool in providing chemical (molecular) information from the solid samples collected by the rover, with a particular focus on the char-acterization of the organic content. The core of the MOMA instrument is a gas chromatograph coupled with a mass spectrometer (GC-MS) which provides the unique capability to characterize a broad range of compounds, including both of volatile and non-volatile species. Samples will be crushed and deposited into sample cups seated in a rotating carousel. Soil samples will be analyzed either by UV laser desorption / ionization (LDI) or pyrolysis gas chromatography ion trap mass spectrometry (pyr-GC-ITMS).The French GC brassboard was coupled to the US ion trap mass spectrometer brassboard in a flight-like con-figuration for several coupling campains. The MOMA GC setup is based on the SAM heritage design with a He reservoir and 4 separate analytical modules including traps, columns and Thermal Conductivity Detectors. Solid samples are sealed and heated in this setup using a manual tapping station, designed and built at MPS in Germany, for GC-MS analysis. The gaseous species eluting from the GC are then ionized by an electron impact ionization source in the MS chamber and analyzed by the linear ion trap mass spectrometer. Volatile and non-volatile compounds were injected in the MOMA instrumental suite. Both of these compounds classes were detected by the TCD and by the MS. MS signal (total ion current) and single mass spectra by comparison with the NIST library, gave us an unambiguous confirmation of these identifications. The mass spectra arise from an average of 10 mass spectra averaged around a given time point in the total ion chromatogram.Based on commercial instrument, the MOMA requirement for sensitivity in the GC-MS mode for organic molecules is 1 pmol. In this test, sensitivity was determined for the GC TCD and MS response to a dilution

Protein chemical characterization of Gc globulin (vitamin D-binding protein) isoforms; Gc-1f, Gc-1s and Gc-2

DEFF Research Database (Denmark)

Christiansen, Maja; Jørgensen, Charlotte S; Laursen, Inga

2007-01-01

-survival of patients with fulminant hepatic failure and trauma. Here, we characterize the dominant isoforms of plasma-derived Gc globulin from Cohn fraction IV paste with respect to amino acid sequence and posttranslational modifications. Gc globulin was purified in large scale and the isoforms separated by ion...

Performance of the future MOMA GC-ITMS instrument

Science.gov (United States)

Grand, Noel; Buch, Arnaud; Veronica, Pinnick; Szopa, Cyril; Danell, Ryan; Van Amerom, Friso H. W.; Glavin, Daniel P.; Freissinet, Caroline; Arevalo, Ricardo; Stalport, Fabien; Getty, Stephanie; Coll, Patrice; Steinninger, Harald; Brinckerhoff, William; Mahaffy, Paul; Goesmann, Fred; Raulin, F.; Goetz, Walter; MOMA Team

2016-10-01

The Mars Organic Molecule Analyzer (MOMA) experiment aboard the future ExoMars mission will be the continuation of the SAM expirement aboard the Curiosity rover, with the search for the organic composition of the Mars surface. With ExoMars the sample will be extracted as deep as 2 meters below the martian surface to minimize effects of radiation and oxidation on organic materials. To analyze the wide range of organic composition (volatile and non-volatiles compounds) of the Martian soil MOMA is composed with an UV laser desorption / ionization (LDI) and a pyrolysis gas chromatography ion trap mass spectrometry (pyr-GC-ITMS). In order to analyze refractory organic compounds and chirality samples which undergo GC-ITMS analysis may be submitted to a derivatization process, consisting of the reaction of the sample components with specific reactants (MTBSTFA [1], DMF-DMA [2] or TMAH [3]).To optimize and test the performance of the GC-ITMS instrument we have performed several coupling tests campaigns between the GC, providing by the French team (LISA, LATMOS, CentraleSupelec), and the MS, providing by the US team (NASA, GSFC). Last campaign has been done with the ETU models which is similar to the flight model and which include the oven and the taping station providing by the German team (MPS).The results obtained demonstrate the current status of the end-to-end performance of the gas chromatography-mass spectrometry mode of operation.

Surface modification of g-C3N4 by hydrazine: Simple way for noble-metal free hydrogen evolution catalysts

KAUST Repository

Chen, Yin

2015-11-02

The graphitic carbon nitride (g-C3N4) usually is thought to be an inert material and it’s difficult to have the surface terminated NH2 groups functionalized. By modifying the g-C3N4 surface with hydrazine, the diazanyl group was successfully introduced onto the g-C3N4 surface, which allows the introduction with many other function groups. Here we illustrated that by reaction of surface hydrazine group modified g-C3N4 with CS2 under basic condition, a water electrolysis active group C(=S)SNi can be implanted on the g-C3N4 surface, and leads to a noble metal free hydrogen evolution catalyst. This catalyst has 40% hydrogen evolution efficiency compare to the 3 wt% Pt photo precipitated g-C3N4, with only less than 0.2 wt% nickel.

Surface modification of g-C3N4 by hydrazine: Simple way for noble-metal free hydrogen evolution catalysts

KAUST Repository

Chen, Yin; Lin, Bin; Wang, Hong; Yang, Yong; Zhu, Haibo; Yu, Weili; Basset, Jean-Marie

2015-01-01

The graphitic carbon nitride (g-C3N4) usually is thought to be an inert material and it’s difficult to have the surface terminated NH2 groups functionalized. By modifying the g-C3N4 surface with hydrazine, the diazanyl group was successfully introduced onto the g-C3N4 surface, which allows the introduction with many other function groups. Here we illustrated that by reaction of surface hydrazine group modified g-C3N4 with CS2 under basic condition, a water electrolysis active group C(=S)SNi can be implanted on the g-C3N4 surface, and leads to a noble metal free hydrogen evolution catalyst. This catalyst has 40% hydrogen evolution efficiency compare to the 3 wt% Pt photo precipitated g-C3N4, with only less than 0.2 wt% nickel.

Theoretical study of GC+/GC base pair derivatives

International Nuclear Information System (INIS)

Meng Fancui; Wang Huanjie; Xu Weiren; Liu Chengbu

2005-01-01

The geometries of R (R=CH 3 , CH 3 O, F, NO 2 ) substituted GC base pair derivatives and their cations have been optimized at B3LYP/6-31G* level and the substituent effects on the neutral and cationic geometric structures and energies have been discussed. The inner reorganization energies of various base pair derivatives and the native GC base pair have been calculated to discuss the substituent effects on the reorganization energy. NBO (natural bond orbital) analysis has been carried out on both the neutral and the cationic systems to investigate the differences of the charge distributions and the electronic structures. The outcomes indicate that 8-CH 3 O-G:C has the greatest reorganization energy and 8-NO 2 -G:C has the least, while the other substituted base pairs have a reorganization energy close to that of G:C. The one charge is mostly localized on guanine part after ionization and as high as 0.95e. The bond distances of N1-N3'andN2-O2' in the cationic base pair derivatives shortened and that of O6-N4' elongated as compared with the corresponding bond distances of the neutral GC base pair derivatives

Detection of gamma-irradiated peanuts by ESR spectroscopy and GC analysis of hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Wei Mingli; An Li [Institute of Agro-food Science and Technology, Chinese Academy of Agricultural Sciences, 100193 Beijing (China); Yi Mingha, E-mail: wangyilwm@163.co [Institute of Agro-food Science and Technology, Chinese Academy of Agricultural Sciences, 100193 Beijing (China); Feng Wang [Institute of Agro-food Science and Technology, Chinese Academy of Agricultural Sciences, 100193 Beijing (China); Yan Lizhang [Division of Metrology in Ionizing Radiation and Medicine, National Institute of Metrology, 100013 Beijing (China)

2011-03-15

Peanuts were analyzed by electron spin resonance (ESR) spectroscopy and gas chromatography (GC) before and after gamma irradiation. Using European protocols, the validity and effectiveness of these two techniques were compared with regard to sample preparation, sample and solvent consumption and dose-response curves after irradiation. The results showed the possibility of using ESR and GC for distinguishing between irradiated and unirradiated peanuts. A radiation dose of 0.1 kGy could be detected by ESR but not by GC. The results also indicated that GC is an effective method for qualitative analysis of irradiated peanut, while ESR is suitable for the rapid detection of irradiated peanuts.

Advanced Characterization of Semivolatile Organic Compounds Emitted from Biomass Burning

Science.gov (United States)

Hatch, L. E.; Liu, Y.; Rivas-Ubach, A.; Shaw, J. B.; Lipton, M. S.; Barsanti, K. C.

2017-12-01

Biomass burning (BB) emits large amounts of non-methane organic gases (NMOGs) and primary (directly emitted) particulate matter (PM). NMOGs also react in plume to form secondary PM (i.e., SOA) and ozone. BB-PM has been difficult to represent accurately in models used for chemistry and climate predictions, including for air quality and fire management purposes. Much recent research supports that many previously unconsidered SOA precursors exist, including oxidation of semivolatile compounds (SVOCs). Although many recent studies have characterized relatively volatile BB-derived NMOGs and relatively non-volatile particle-phase organic species, comparatively few studies have performed detailed characterization of SVOCs emitted from BB. Here we present efforts to expand the volatility and compositional ranges of compounds measured in BB smoke. In this work, samples of SVOCs in gas and particle phases were collected from 18 fires representing a range of fuel types during the 2016 FIREX fire laboratory campaign; samples were analyzed by two-dimensional gas chromatography with time-of-flight mass spectrometry (GCxGC-TOFMS) and Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS). Hundreds of compounds were detectable in both gas and particle phases by GCxGC-TOFMS whereas thousands of peaks were present in the FTICR mass spectra. Data from both approaches highlight that chemical fingerprints of smoke are fuel/burn-dependent. These efforts support our continued research in building the understanding and model representation of BB emissions and BB-derived SOA.

Recognition of beer brand based on multivariate analysis of volatile fingerprint.

Science.gov (United States)

Cajka, Tomas; Riddellova, Katerina; Tomaniova, Monika; Hajslova, Jana

2010-06-18

Automated head-space solid-phase microextraction (HS-SPME)-based sampling procedure, coupled to gas chromatography-time-of-flight mass spectrometry (GC-TOFMS), was developed and employed for obtaining of fingerprints (GC profiles) of beer volatiles. In total, 265 speciality beer samples were collected over a 1-year period with the aim to distinguish, based on analytical (profiling) data, (i) the beers labelled as Rochefort 8; (ii) a group consisting of Rochefort 6, 8, 10 beers; and (iii) Trappist beers. For the chemometric evaluation of the data, partial least squares discriminant analysis (PLS-DA), linear discriminant analysis (LDA), and artificial neural networks with multilayer perceptrons (ANN-MLP) were tested. The best prediction ability was obtained for the model that distinguished a group of Rochefort 6, 8, 10 beers from the rest of beers. In this case, all chemometric tools employed provided 100% correct classification. Slightly worse prediction abilities were achieved for the models "Trappist vs. non-Trappist beers" with the values of 93.9% (PLS-DA), 91.9% (LDA) and 97.0% (ANN-MLP) and "Rochefort 8 vs. the rest" with the values of 87.9% (PLS-DA) and 84.8% (LDA) and 93.9% (ANN-MLP). In addition to chromatographic profiling, also the potential of direct coupling of SPME (extraction/pre-concentration device) with high-resolution TOFMS employing a direct analysis in real time (DART) ion source has been demonstrated as a challenging profiling approach. Copyright (c) 2010 Elsevier B.V. All rights reserved.

A high area, porous and resistant platinized stainless steel fiber coated by nanostructured polypyrrole for direct HS-SPME of nicotine in biological samples prior to GC-FID quantification.

Science.gov (United States)

Abdolhosseini, Sana; Ghiasvand, Alireza; Heidari, Nahid

2017-09-01

The surface of a stainless steel fiber was made porous, resistant and cohesive using electrophoretic deposition and coated by the nanostructured polypyrrole using an amended in-situ electropolymerization method. The coated fiber was applied for direct extraction of nicotine in biological samples through a headspace solid-phase microextraction (HS-SPME) method followed by GC-FID determination. The effects of the important experimental variables on the efficiency of the developed HS-SPME-GC-FID method, including pH of sample solution, extraction temperature and time, stirring rate, and ionic strength were evaluated and optimized. Under the optimal experimental conditions, the calibration curve was linear over the range of 0.1-20μgmL -1 and the detection limit was obtained 20ngmL -1 . Relative standard deviation (RSD, n=6) was calculated 7.6%. The results demonstrated the superiority of the proposed fiber compared with the most used commercial types. The proposed HS-SPME-GC-FID method was successfully used for the analysis of nicotine in urine and human plasma samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Immunotherapy for Prostate Cancer with Gc Protein-Derived Macrophage-Activating Factor, GcMAF.

Science.gov (United States)

Yamamoto, Nobuto; Suyama, Hirofumi; Yamamoto, Nobuyuki

2008-07-01

Serum Gc protein (known as vitamin D(3)-binding protein) is the precursor for the principal macrophage-activating factor (MAF). The MAF precursor activity of serum Gc protein of prostate cancer patients was lost or reduced because Gc protein was deglycosylated by serum alpha-N-acetylgalactosaminidase (Nagalase) secreted from cancerous cells. Therefore, macrophages of prostate cancer patients having deglycosylated Gc protein cannot be activated, leading to immunosuppression. Stepwise treatment of purified Gc protein with immobilized beta-galactosidase and sialidase generated the most potent MAF (termed GcMAF) ever discovered, which produces no adverse effect in humans. Macrophages activated by GcMAF develop a considerable variation of receptors that recognize the abnormality in malignant cell surface and are highly tumoricidal. Sixteen nonanemic prostate cancer patients received weekly administration of 100 ng of GcMAF. As the MAF precursor activity increased, their serum Nagalase activity decreased. Because serum Nagalase activity is proportional to tumor burden, the entire time course analysis for GcMAF therapy was monitored by measuring the serum Nagalase activity. After 14 to 25 weekly administrations of GcMAF (100 ng/week), all 16 patients had very low serum Nagalase levels equivalent to those of healthy control values, indicating that these patients are tumor-free. No recurrence occurred for 7 years.

Outbreak of Ips nitidus and Ips shangrila in northeastern margin of the Tibetan Plateau

Czech Academy of Sciences Publication Activity Database

Jakuš, R.; Kalinová, Blanka; Hoskovec, Michal; Knížek, M.; Schlyter, F.; Sun, J.-H.; Zhang, Q. H.

2011-01-01

Roč. 89, - (2011), s. 111-117 ISSN 1436-1566 R&D Projects: GA MŠk ME 860 Institutional research plan: CEZ:AV0Z40550506 Keywords : Ips shangrila * Ips nitidus * pheromone s * GCxGC-TOFMS Subject RIV: CC - Organic Chemistry

Analysis of pesticide residues in strawberries and soils by GC-MS/MS, LC-MS/MS and two-dimensional GC-time-of-flight MS comparing organic and integrated pest management farming.

Science.gov (United States)

Fernandes, Virgínia C; Lehotay, Steven J; Geis-Asteggiante, Lucía; Kwon, Hyeyoung; Mol, Hans G J; van der Kamp, Henk; Mateus, Nuno; Domingues, Valentina F; Delerue-Matos, Cristina

2014-01-01

This study analysed 22 strawberry and soil samples after their collection over the course of 2 years to compare the residue profiles from organic farming with integrated pest management practices in Portugal. For sample preparation, we used the citrate-buffered version of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. We applied three different methods for analysis: (1) 27 pesticides were targeted using LC-MS/MS; (2) 143 were targeted using low pressure GC-tandem mass spectrometry (LP-GC-MS/MS); and (3) more than 600 pesticides were screened in a targeted and untargeted approach using comprehensive, two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF-MS). Comparison was made of the analyses using the different methods for the shared samples. The results were similar, thereby providing satisfactory confirmation of both similarly positive and negative findings. No pesticides were found in the organic-farmed samples. In samples from integrated pest management practices, nine pesticides were determined and confirmed to be present, ranging from 2 µg kg(-1) for fluazifop-p-butyl to 50 µg kg(-1) for fenpropathrin. Concentrations of residues in strawberries were less than European maximum residue limits.

Qualitative analyses of less-volatile organic molecules from female skin scents by comprehensive two dimensional gas chromatography-time of flight mass spectrometry

Czech Academy of Sciences Publication Activity Database

Doležal, P.; Kyjaková, Pavlína; Valterová, Irena; Urban, Š.

2017-01-01

Roč. 1505, Jul 7 (2017), s. 77-86 ISSN 0021-9673. [International Symposium on Capillary Chromatography /40./ and GCxGC Symposium /13./. Riva del Garda, 29.05.2016-03.06.2016] Institutional support: RVO:61388963 Keywords : human scent analysis * molecular composition of human scent * forensic chemistry * human scent signature * GCxGC-TOFMS Subject RIV: CB - Analytical Chemistry , Separation OBOR OECD: Analytical chemistry Impact factor: 3.981, year: 2016

Drop-on-demand sample introduction system coupled with the flowing atmospheric-pressure afterglow for direct molecular analysis of complex liquid microvolume samples.

Science.gov (United States)

Schaper, J Niklas; Pfeuffer, Kevin P; Shelley, Jacob T; Bings, Nicolas H; Hieftje, Gary M

2012-11-06

One of the fastest developing fields in analytical spectrochemistry in recent years is ambient desorption/ionization mass spectrometry (ADI-MS). This burgeoning interest has been due to the demonstrated advantages of the method: simple mass spectra, little or no sample preparation, and applicability to samples in the solid, liquid, or gaseous state. One such ADI-MS source, the flowing atmospheric-pressure afterglow (FAPA), is capable of direct analysis of solids just by aiming the source at the solid surface and sampling the produced ions into a mass spectrometer. However, direct introduction of significant volumes of liquid samples into this source has not been possible, as solvent loads can quench the afterglow and, thus, the formation of reagent ions. As a result, the analysis of liquid samples is preferably carried out by analyzing dried residues or by desorbing small amounts of liquid samples directly from the liquid surface. In the former case, reproducibility of sample introduction is crucial if quantitative results are desired. In the present study, introduction of liquid samples as very small droplets helps overcome the issues of sample positioning and reduced levels of solvent intake. A recently developed "drop-on-demand" (DOD) aerosol generator is capable of reproducibly producing very small volumes of liquid (∼17 pL). In this paper, the coupling of FAPA-MS and DOD is reported and applications are suggested. Analytes representing different classes of substances were tested and limits of detections were determined. Matrix tolerance was investigated for drugs of abuse and their metabolites by analyzing raw urine samples and quantification without the use of internal standards. Limits of detection below 2 μg/mL, without sample pretreatment, were obtained.

Intraspecific variation of cuticular hydrocarbon profiles in the Anastrepha fraterculus (Diptera: Tephritidae) species complex

Czech Academy of Sciences Publication Activity Database

Vaníčková, Lucie; Břízová, Radka; Mendonca, A. L.; Pompeiano, A.; do Nascimento, R. R.

2015-01-01

Roč. 139, č. 9 (2015), s. 679-689 ISSN 0931-2048 Institutional support: RVO:61388963 Keywords : chemotaxonomy * GCxGC/TOFMS * multiple factorial analyses * putative species * South American fruit fly Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 1.517, year: 2015

Analysis of Biogenic Amines by GC/FID and GC/MS

OpenAIRE

Nakovich, Laura

2003-01-01

Low levels of biogenic amines occur naturally, but high levels (FDA sets 50 ppm of histamine in fish as the maximum allowable level) can lead to scombroid poisoning. Amines in general are difficult to analyze by Gas Chromatography (GC) due to their lack of volatility and their interaction with the GC column, often leading to significant tailing and poor reproducibility. Biogenic amines need to be derivatized before both GC and HPLC analyses. The objective of this research was to devel...

Towards comprehensive hydrocarbons analysis of middle distillates by LC-GCxGC.

Science.gov (United States)

Adam, Frédérick; Bertoncini, Fabrice; Thiébaut, Didier; Esnault, Sébastien; Espinat, Didier; Hennion, M C

2007-01-01

The detailed characterization of middle distillates is essential for a better understanding of reactions involved in refining processes. Owing to a higher resolution power and an enhanced sensitivity, but especially to a group-type ordering in the chromatographic plane, comprehensive two-dimensional gas chromatography (GCxGC) offers unsurpassed characterization possibilities for petroleum samples. However, GCxGC fails to totally discriminate naphthenes from unsaturates occurring in hydrotreated diesel samples. This article aims at promoting the implementation of LC-GCxGC for the quantitative determination of hydrocarbon distribution in middle distillates, including naphthenes. In this configuration, liquid chromatography (LC) enables the separation of hydrocarbons into two fractions (viz., saturated and unsaturated) before the subsequent analysis of each fraction by GCxGC. In this paper, the choice of GCxGC conditions in order to achieve the separation and identification of hydrocarbons by chemical class is discussed; under these conditions, naphthenes are separated according to the number of saturated rings. For the first time, the presence of di-, tri-, and tetra-naphthenes resulting from the hydroconversion of aromatics can clearly be evidenced. A quantitative procedure for the determination of the distribution of hydrocarbons, including the distribution of naphthenes according to the number of saturated rings, is also proposed and discussed in detail. LC-GCxGC is found to provide an unequalled degree of information that will widely contribute to a better understanding of hydroconversion processes.

GENOTYPE DIFFERENCE OF –572 G>C AND -174 G>C IL-6 GENE POLYMORPHISM BETWEEN BALINESE POSTMENOPAUSAL WOMEN WITH OSTEOPOROSIS AND WITHOUT OSTEOPOROSIS

Directory of Open Access Journals (Sweden)

E Yulianto

2013-09-01

Full Text Available Background: Osteoporosis is a silent metabolic disease characterized by diminished bone mass and change in bone microstructure which cause increment of fracture risk. Until now, osteoporosis still becomes one of major health problems around the world. In Indonesia, the incidence of osteoporosisis 25%. Previous study have shown the relation between osteoporosis and IL-6 gene polymorphism at-572G>C and -174 G>C. There are some controversies about the correlation between thesepolymorphism and osteoporosis because of different result between each study. Genotype G polymorphism at -572 G>C of IL-6 gene has been correlated with lower Bone mineral density (BMD and Genotype G polymorphism at -174G>C of IL-6 gene has been correlated with higher BMD value.In Indonesia, there are still no study about the association between IL-6 gene polymorphism and osteoporosis. In the future this IL-6 gene polymorphism could be used as a genetic marker for osteoporosis in postmenopausal woman. The objective of this study is to determine the difference ofgenotype of -572G>C and -174G>C polymorphism of IL-6 gene and osteoporosis in Balinese postmenopausal women.Method: This research design is a case control study. Sample was obtained at orthopedic outpatient clinic of Sanglah General Hospital, Bali-Indonesia from June 2012 untilNovember 2012. The diagnosis of osteoporosis is described as BMD value with T score ≤ -2.5 SDusing DEXA. All sample’s peripheral blood are taken to be isolated for DNA and analyzed for IL-6 gene polymorphism at -572G>C and -174G>C using Real Time PCR. Data obtained was analyzed with chi square test using SPSS.Results: This research found 11 osteoporosis sample from total 52 with no difference sample characteristic between case and control (p > 0.05. Using Chi square test,There was a significant differences between genotype -572 G>C; IL-6 gene polymorphism in Balinese postmenopausal woman with osteoporosis and in Balinese

Metabolite profiling approach reveals the interface of primary and secondary metabolism in colored cauliflowers (Brassica oleracea L. ssp. botrytis).

Science.gov (United States)

Park, Soo-Yun; Lim, Sun-Hyung; Ha, Sun-Hwa; Yeo, Yunsoo; Park, Woo Tae; Kwon, Do Yeon; Park, Sang Un; Kim, Jae Kwang

2013-07-17

In the present study, carotenoids, anthocyanins, and phenolic acids of cauliflowers ( Brassica oleracea L. ssp. botrytis) with various colored florets (white, yellow, green, and purple) were characterized to determine their phytochemical diversity. Additionally, 48 metabolites comprising amino acids, organic acids, sugars, and sugar alcohols were identified using gas chromatography-time-of-flight mass spectrometry (GC-TOFMS). Carotenoid content was considerably higher in green cauliflower; anthocyanins were detected only in purple cauliflower. Phenolic acids were higher in both green and purple cauliflower. Results of partial least-squares discriminant, Pearson correlation, and hierarchical clustering analyses showed that green cauliflower is distinct on the basis of the high levels of amino acids and clusters derived from common or closely related biochemical pathways. These results suggest that GC-TOFMS-based metabolite profiling, combined with chemometrics, is a useful tool for determining phenotypic variation and identifying metabolic networks connecting primary and secondary metabolism.

Qualitative/Chemical Analyses of Ankaferd Hemostat and Its Antioxidant Content in Synthetic Gastric Fluids

Directory of Open Access Journals (Sweden)

Ahmet Koluman

2016-01-01

Full Text Available Introduction. Ankaferd hemostat (ABS is the first topical haemostatic agent involving the red blood cell-fibrinogen interactions. The antihemorrhagic efficacy of ABS has been tested in controlled clinical trials. The drug induces the formation of an encapsulated complex protein web with vital erythroid aggregation. The aim of this study is to detect the essential toxicity profile and the antioxidant molecules inside ABS. Methods. The pesticides were analyzed by GC-MS and LC-MS. The determination by ICP-MS after pressure digestion was performed for the heavy metals. HPLC was used for the detection of mycotoxins. Dioxin Response Chemically Activated Luciferase Gene Expression method was used for the dioxin evaluation. TOF-MS and spectra data were evaluated to detect the antioxidants and other molecules. Results. TOF-MS spectra revealed the presence of several antioxidant molecules (including tocotrienols, vitamin E, tryptophan, estriol, galangin, apigenin, oenin, 3,4-divanillyltetrahydrofuran, TBHQ, thymol, BHA, BHT, lycopene, glycyrrhetinic acid, and tomatine, which may have clinical implications in the pharmacobiological actions of ABS. Conclusion. The safety of ABS regarding the presence of heavy metals, pesticides, mycotoxins, GMO and dioxins, and PCBs was demonstrated. Thus the present toxicological results indicated the safety of ABS. The antioxidant content of ABS should be investigated in future studies.

Immunotherapy for Prostate Cancer with Gc Protein-Derived Macrophage-Activating Factor, GcMAF1

Science.gov (United States)

Yamamoto, Nobuto; Suyama, Hirofumi; Yamamoto, Nobuyuki

2008-01-01

Serum Gc protein (known as vitamin D3-binding protein) is the precursor for the principal macrophage-activating factor (MAF). The MAF precursor activity of serum Gc protein of prostate cancer patients was lost or reduced because Gc protein was deglycosylated by serum α-N-acetylgalactosaminidase (Nagalase) secreted from cancerous cells. Therefore, macrophages of prostate cancer patients having deglycosylated Gc protein cannot be activated, leading to immunosuppression. Stepwise treatment of purified Gc protein with immobilized β-galactosidase and sialidase generated the most potent MAF (termed GcMAF) ever discovered, which produces no adverse effect in humans. Macrophages activated by GcMAF develop a considerable variation of receptors that recognize the abnormality in malignant cell surface and are highly tumoricidal. Sixteen nonanemic prostate cancer patients received weekly administration of 100 ng of GcMAF. As the MAF precursor activity increased, their serum Nagalase activity decreased. Because serum Nagalase activity is proportional to tumor burden, the entire time course analysis for GcMAF therapy was monitored by measuring the serum Nagalase activity. After 14 to 25 weekly administrations of GcMAF (100 ng/week), all 16 patients had very low serum Nagalase levels equivalent to those of healthy control values, indicating that these patients are tumor-free. No recurrence occurred for 7 years. PMID:18633461

Extractionless GC/MS analysis of gamma-hydroxybutyrate and gamma-butyrolactone with trifluoroacetic anhydride and heptafluoro-1-butanol from aqueous samples.

Science.gov (United States)

Sabucedo, Alberto J; Furton, Kenneth G

2004-06-01

gamma-Hydroxybutyrate (GHB) is a DEA Schedule I drug of abuse commonly spiked into beverages to incapacitate victims of sexual assault. GHB is a challenging drug for analysis by GC/MS because of its small size, charged nature, low volatility, and intramolecular esterification leading to gamma-butyrolactone (GBL). In this work an extractionless technique has been developed that allows for the use of an aqueous sample for direct derivatization. The technique uses a solution of trifluoroacetic anhydride (TFAA) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (HFB) to derivatize the active hydrogens of GHB. The conversion of GBL into GHB can be forced under alkaline conditions by diluting the sample in 10 mM borate buffer, pH 12. GBL found in beverages intended for human consumption is treated as a Schedule I control substance analogue. Spikes of the two compounds into several beverage matrices gave quantitative recovery of GHB by GC/MS. The derivatization produces higher molecular mass products whose fragmentation pattern provides multiple peaks for confirmation and quantification. The concentration of GBL can also be indirectly determined by the method developed. Therefore, this extractionless technique is rapid, sensitive, and selective for the confirmation of the presence of GHB and GBL in commercial beverages.

Preparation of Gc protein-derived macrophage activating factor (GcMAF) and its structural characterization and biological activities.

Science.gov (United States)

Mohamad, Saharuddin Bin; Nagasawa, Hideko; Uto, Yoshihiro; Hori, Hitoshi

2002-01-01

Gc protein has been reported to be a precursor of Gc protein-derived macrophage activation factor (GcMAF) in the inflammation-primed macrophage activation cascade. An inducible beta-galactosidase of B cells and neuraminidase of T cells convert Gc protein to GcMAF. Gc protein from human serum was purified using 25(OH)D3 affinity column chromatography and modified to GcMAF using immobilized glycosidases (beta-galactosidase and neuraminidase) The sugar moiety structure of GcMAF was characterized by lectin blotting by Helix pomatia agglutinin. The biological activities of GcMAF were evaluated by a superoxide generation assay and a phagocytosis assay. We successfully purified Gc protein from human serum. GcMAF was detected by lectin blotting and showed a high biological activity. Our results support the importance of the terminal N-acetylgalactosamine moiety in the GcMAF-mediated macrophage activation cascade, and the existence of constitutive GcMAF in human serum. These preliminary data are important for designing small molecular GcMAF mimics.

Development of the GC-MS organic aerosol monitor (GC-MS OAM) for in-field detection of particulate organic compounds

Science.gov (United States)

Cropper, Paul M.; Overson, Devon K.; Cary, Robert A.; Eatough, Delbert J.; Chow, Judith C.; Hansen, Jaron C.

2017-11-01

Particulate matter (PM) is among the most harmful air pollutants to human health, but due to its complex chemical composition is poorly characterized. A large fraction of PM is composed of organic compounds, but these compounds are not regularly monitored due to limitations in current sampling and analysis techniques. The Organic Aerosol Monitor (GC-MS OAM) combines a collection device with thermal desorption, gas chromatography and mass spectrometry to quantitatively measure the carbonaceous components of PM on an hourly averaged basis. The GC-MS OAM is fully automated and has been successfully deployed in the field. It uses a chemically deactivated filter for collection followed by thermal desorption and GC-MS analysis. Laboratory tests show that detection limits range from 0.2 to 3 ng for 16 atmospherically relevant compounds, with the possibility for hundreds more. The GC-MS OAM was deployed in the field for semi-continuous measurement of the organic markers, levoglucosan, dehydroabietic acid, and polycyclic aromatic hydrocarbons (PAHs) from January to March 2015. Results illustrate the significance of this monitoring technique to characterize the organic components of PM and identify sources of pollution.

Middle distillates hydrogen content via GC×GC-FID.

Science.gov (United States)

Vozka, Petr; Mo, Huaping; Šimáček, Pavel; Kilaz, Gozdem

2018-08-15

Liquid transportation fuels in the middle distillate range contain thousands of hydrocarbons making the predictions and calculations of properties from composition a challenging process. We present a new approach of hydrogen content determination by comprehensive two-dimensional gas chromatography with flame ionization detector (GC×GC-FID) using a weighted average method. GC×GC-FID hydrogen determination precision was excellent (0.005 wt% repeatability). The method accuracy was evaluated by high-resolution nuclear magnetic resonance (NMR) technique, which is non-biased, measures the H signal directly and was independently validated by controls in the current study. The hydrogen content (in the range of 12.72-15.54 wt%) in 28 fuel samples were determined using GC×GC-FID. Results were within ± 2% of those obtained via NMR. Owing to the fact that NMR is accepted as an accurate technique for hydrogen content determination, the GC×GC method proposed in this study can be considered precise and accurate. Copyright © 2018 Elsevier B.V. All rights reserved.

Experimental study of laser ablation as sample introduction technique for inductively coupled plasma-mass spectrometry

International Nuclear Information System (INIS)

Van Winckel, S.

2001-01-01

The contribution consists of an abstract of a PhD thesis. In the PhD study, several complementary applications of laser-ablation were investigated in order to characterise experimentally laser ablation (LA) as a sample introduction technique for ICP-MS. Three applications of LA as a sample introduction technique are discussed: (1) the microchemical analysis of the patina of weathered marble; (2) the possibility to measure isotope ratios (in particular Pb isotope ratios in archaeological bronze artefacts); and (3) the determination of Si in Al as part of a dosimetric study of the BR2 reactor vessel

Postmortem identification and quantitation of 2,5-dimethoxy-4-n-propylthiophenethylamine using GC-MSD and GC-NPD.

Science.gov (United States)

Curtis, Byron; Kemp, Philip; Harty, Linda; Choi, Chai; Christensen, Dix

2003-10-01

2,5-Dimethoxy-4-n-propylthiophenethylamine (2C-T-7) has structural and pharmacodynamic similarities to methylenedioxymethamphetamine (MDMA). This compound was initially identified from a routine screening procedure in postmortem urine from a 20-year-old male that died in a local emergency room after reportedly insufflating 35 mg. This report describes the development of a quantitative method for 2C-T-7. A number of method parameters were studied including internal standard selection, liquid-liquid extraction scheme, and drug stability in preserved refrigerated blood. The adopted method for blood and urine involves the addition of trimethoxyamphetamine (TMA) as internal standard, alkalinization with ammonium hydroxide, and liquid-liquid extraction with n-chlorobutane. To facilitate recovery from liver, a 1:4 aqueous homogenate was pretreated with dilute perchloric acid, centrifuged, and the supernatant was extracted as previously described. In each case, 0.1% hydrochloric acid in methanol was added during the final concentration step to prevent loss of drug caused by evaporation. Samples were analyzed by gas chromatography with nitrogen-phosphorus detection (GC-NPD) and electron ionization GC-mass spectrometry (MS) utilizing selected ion monitoring. For the GC-MS analysis, the characteristic ions monitored for 2C-T-7 were m/z 226, 255, and 183 and for TMA, m/z 182. The limits of detection and quantitation in blood were 6.0 and 15.6 ng/mL, respectively, by both GC-NPD and GC-MS. The results from the postmortem case were as follows: heart blood, 57 ng/mL; femoral blood, 100 ng/mL; urine, 1120 ng/mL; and liver, 854 ng/g.

Purification of equine Gc-globulin

DEFF Research Database (Denmark)

Houen, Gunnar; Pihl, Tina Holberg; Andersen, Pia Haubro

Objectives With the aim of producing antibodies for an equine Group specific component (Gc)-globulin assay, the protein was purified from normal equine plasma. Methods Equine Gc-globulin was purified from healthy horse plasma using ion exchange chromatography (Q-Sepharose, CM......-Sepharose) and preparative PAGE. Results Equine Gc-globulin has successfully been purified from healthy horse plasma and rabbits and mice are being immunized to produce specific antibodies. Conclusions Purification of equine Gc-globulin and the production of specific antibodies will make it possible to develop an assay...... to be a sensitive marker of acute tissue injury and fatal outcome in humans. Patients with a low plasma concentration of Gc-globulin due to severe tissue injury might potentially benefit from infusions with purified Gc-globulin [1]. With an equine Gc-globulin assay, future studies will investigate the concentration...

Classification of Coffee Beans by GC-C-IRMS, GC-MS, and 1H-NMR

Science.gov (United States)

Arana, Victoria Andrea; Esseiva, Pierre; Pazos, Diego

2016-01-01

In a previous work using 1H-NMR we reported encouraging steps towards the construction of a robust expert system for the discrimination of coffees from Colombia versus nearby countries (Brazil and Peru), to assist the recent protected geographical indication granted to Colombian coffee in 2007. This system relies on fingerprints acquired on a 400 MHz magnet and is thus well suited for small scale random screening of samples obtained at resellers or coffee shops. However, this approach cannot easily be implemented at harbour's installations, due to the elevated operational costs of cryogenic magnets. This limitation implies shipping the samples to the NMR laboratory, making the overall approach slower and thereby more expensive and less attractive for large scale screening at harbours. In this work, we report on our attempt to obtain comparable classification results using alternative techniques that have been reported promising as an alternative to NMR: GC-MS and GC-C-IRMS. Although statistically significant information could be obtained by all three methods, the results show that the quality of the classifiers depends mainly on the number of variables included in the analysis; hence NMR provides an advantage since more molecules are detected to obtain a model with better predictions. PMID:27516919

Classification of Coffee Beans by GC-C-IRMS, GC-MS, and (1)H-NMR.

Science.gov (United States)

Arana, Victoria Andrea; Medina, Jessica; Esseiva, Pierre; Pazos, Diego; Wist, Julien

2016-01-01

In a previous work using (1)H-NMR we reported encouraging steps towards the construction of a robust expert system for the discrimination of coffees from Colombia versus nearby countries (Brazil and Peru), to assist the recent protected geographical indication granted to Colombian coffee in 2007. This system relies on fingerprints acquired on a 400 MHz magnet and is thus well suited for small scale random screening of samples obtained at resellers or coffee shops. However, this approach cannot easily be implemented at harbour's installations, due to the elevated operational costs of cryogenic magnets. This limitation implies shipping the samples to the NMR laboratory, making the overall approach slower and thereby more expensive and less attractive for large scale screening at harbours. In this work, we report on our attempt to obtain comparable classification results using alternative techniques that have been reported promising as an alternative to NMR: GC-MS and GC-C-IRMS. Although statistically significant information could be obtained by all three methods, the results show that the quality of the classifiers depends mainly on the number of variables included in the analysis; hence NMR provides an advantage since more molecules are detected to obtain a model with better predictions.

Immunotherapy for Prostate Cancer with Gc Protein-Derived Macrophage-Activating Factor, GcMAF1

OpenAIRE

Yamamoto, Nobuto; Suyama, Hirofumi; Yamamoto, Nobuyuki

2008-01-01

Serum Gc protein (known as vitamin D3-binding protein) is the precursor for the principal macrophage-activating factor (MAF). The MAF precursor activity of serum Gc protein of prostate cancer patients was lost or reduced because Gc protein was deglycosylated by serum α-N-acetylgalactosaminidase (Nagalase) secreted from cancerous cells. Therefore, macrophages of prostate cancer patients having deglycosylated Gc protein cannot be activated, leading to immunosuppression. Stepwise treatment of pu...

Atmospheric pressure gas chromatography-time-of-flight-mass spectrometry (APGC-ToF-MS) for the determination of regulated and emerging contaminants in aqueous samples after stir bar sorptive extraction (SBSE).

Science.gov (United States)

Pintado-Herrera, Marina G; González-Mazo, Eduardo; Lara-Martín, Pablo A

2014-12-03

This work presents the development, optimization and validation of a multi-residue method for the simultaneous determination of 102 contaminants, including fragrances, UV filters, repellents, endocrine disruptors, biocides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and several types of pesticides in aqueous matrices. Water samples were processed using stir bar sorptive extraction (SBSE) after the optimization of several parameters: agitation time, ionic strength, presence of organic modifiers, pH, and volume of the derivatizing agent. Target compounds were extracted from the bars by liquid desorption (LD). Separation, identification and quantification of analytes were carried out by gas chromatography (GC) coupled to time-of-flight (ToF-MS) mass spectrometry. A new ionization source, atmospheric pressure gas chromatography (APGC), was tested. The optimized protocol showed acceptable recovery percentages (50-100%) and limits of detection below 1ngL(-1) for most of the compounds. Occurrence of 21 out of 102 analytes was confirmed in several environmental aquatic matrices, including seawater, sewage effluent, river water and groundwater. Non-target compounds such as organophosphorus flame retardants were also identified in real samples by accurate mass measurement of their molecular ions using GC-APGC-ToF-MS. To the best of our knowledge, this is the first time that this technique has been applied for the analysis of contaminants in aquatic systems. By employing lower energy than the more widely used electron impact ionization (EI), AGPC provides significant advantages over EI for those substances very susceptible to high fragmentation (e.g., fragrances, pyrethroids). Copyright © 2014 Elsevier B.V. All rights reserved.

Hydrogen sulfide measurement by headspace-gas chromatography-mass spectrometry (HS-GC-MS): application to gaseous samples and gas dissolved in muscle.

Science.gov (United States)

Varlet, Vincent; Giuliani, Nicole; Palmiere, Cristian; Maujean, Géraldine; Augsburger, Marc

2015-01-01

The aim of our study was to present a new headspace-gas chromatography-mass spectrometry (HS-GC-MS) method applicable to the routine determination of hydrogen sulfide (H(2)S) concentrations in biological and gaseous samples. The primary analytical drawback of the GC/MS methods for H(2)S measurement discussed in the literature was the absence of a specific H(2)S internal standard required to perform quantification. Although a deuterated hydrogen sulfide (D(2)S) standard is currently available, this standard is not often used because this standard is expensive and is only available in the gas phase. As an alternative approach, D(2)S can be generated in situ by reacting deuterated chloride with sodium sulfide; however, this technique can lead to low recovery yield and potential isotopic fractionation. Therefore, N(2)O was chosen for use as an internal standard. This method allows precise measurements of H(2)S concentrations in biological and gaseous samples. Therefore, a full validation using accuracy profile based on the β-expectation tolerance interval is presented. Finally, this method was applied to quantify H(2)S in an actual case of H(2)S fatal intoxication. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Identification of refined petroleum products in contaminated soils using an identification index for GC chromatograms.

Science.gov (United States)

Kwon, Dongwook; Ko, Myoung-Soo; Yang, Jung-Seok; Kwon, Man Jae; Lee, Seung-Woo; Lee, Seunghak

2015-08-01

Hydrocarbons found in the environment are typically characterized by gas chromatography (GC). The shape of the GC chromatogram has been used to identify the source of petroleum contamination. However, the conventional practice of simply comparing the peak patterns of source products to those of environmental samples is dependent on the subjective decisions of individual analysts. We have developed and verified a quantitative analytical method for interpreting GC chromatograms to distinguish refined petroleum products in contaminated soils. We found that chromatograms for gasoline, kerosene, and diesel could be divided into three ranges with boundaries at C6, C8, C16, and C26. In addition, the relative peak area (RPA(GC)) of each range, a dimensionless ratio of the peak area within each range to that of the total range (C6-C26), had a unique value for each petroleum product. An identification index for GC chromatograms (ID(GC)), defined as the ratio of RPA(GC) of C8-C16 to that of C16-C26, was able to identify diesel and kerosene sources in samples extracted from artificially contaminated soils even after weathering. Thus, the ID(GC) can be used to effectively distinguish between refined petroleum products in contaminated soils.

Comprehensive database of Manufactured Gas Plant tars. Part C. Heterocyclic and hydroxylated polycyclic aromatic hydrocarbons.

Science.gov (United States)

Gallacher, Christopher; Thomas, Russell; Lord, Richard; Kalin, Robert M; Taylor, Chris

2017-08-15

Coal tars are a mixture of organic and inorganic compounds that were by-products from the manufactured gas and coke making industries. The tar compositions varied depending on many factors such as the temperature of production and the type of retort used. For this reason a comprehensive database of the compounds found in different tar types is of value to understand both how their compositions differ and what potential chemical hazards are present. This study focuses on the heterocyclic and hydroxylated compounds present in a database produced from 16 different tars from five different production processes. Samples of coal tar were extracted using accelerated solvent extraction (ASE) and derivatized post-extraction using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) with 1% trimethylchlorosilane (TMCS). The derivatized samples were analysed using two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GCxGC/TOFMS). A total of 865 heterocyclic compounds and 359 hydroxylated polycyclic aromatic hydrocarbons (PAHs) were detected in 16 tar samples produced by five different processes. The contents of both heterocyclic and hydroxylated PAHs varied greatly with the production process used, with the heterocyclic compounds giving information about the feedstock used. Of the 359 hydroxylated PAHs detected the majority would not have been be detected without the use of derivatization. Coal tars produced using different production processes and feedstocks yielded tars with significantly different heterocyclic and hydroxylated contents. The concentrations of the individual heterocyclic compounds varied greatly even within the different production processes and provided information about the feedstock used to produce the tars. The hydroxylated PAH content of the samples provided important analytical information that would otherwise not have been obtained without the use of derivatization and GCxGC/TOFMS. Copyright © 2017 John Wiley & Sons, Ltd.

Simultaneous multi-species determination of trimethyllead, monomethylmercury and three butyltin compounds by species-specific isotope dilution GC-ICP-MS in biological samples

Energy Technology Data Exchange (ETDEWEB)

Poperechna, Nataliya; Heumann, Klaus G. [Johannes Gutenberg-University Mainz (Germany). Institute of Inorganic Chemistry and Analytical Chemistry

2005-09-01

An accurate and sensitive multi-species species-specific isotope dilution GC-ICP-MS method was developed for the simultaneous determination of trimethyllead (Me{sub 3}Pb{sup +}), monomethylmercury (MeHg{sup +}) and the three butyltin species Bu{sub 3}Sn{sup +}, Bu{sub 2}Sn{sup 2+}, and BuSn{sup 3+} in biological samples. The method was validated by three biological reference materials (CRM 477, mussel tissue certified for butyltins; CRM 463, tuna fish certified for MeHg{sup +}; DORM 2, dogfish muscle certified for MeHg{sup +}). Under certain conditions, and with minor modifications of the sample pretreatment procedure, this method could also be transferred to environmental samples such as sediments, as demonstrated by analyzing sediment reference material BCR 646 (freshwater sediment, certified for butyltins). The detection limits of the multi-species GC-ICP-IDMS method for biological samples were 1.4 ng g{sup -1} for MeHg{sup +}, 0.06 ng g{sup -1} for Me{sub 3}Pb{sup +}, 0.3 ng g{sup -1} for BuSn{sup 3+} and Bu{sub 3}Sn{sup +}, and 1.2 ng g{sup -1} for Bu{sub 2}Sn{sup 2+}. Because of the high relevance of these heavy metal alkyl species to the quality assurance of seafood, the method was also applied to corresponding samples purchased from a supermarket. The methylated lead fraction in these samples, correlated to total lead, varied over a broad range (from 0.01% to 7.6%). On the other hand, the MeHg{sup +} fraction was much higher, normally in the range of 80-100%. Considering that we may expect tighter legislative limitations on MeHg{sup +} levels in seafood in the future, we found the highest methylmercury contents (up to 10.6 {mu}g g{sup -1}) in two shark samples, an animal which is at the end of the marine food chain, whereas MeHg{sup +} contents of less than 0.2 {mu}g g{sup -1} were found in most other seafood samples; these results correlate with the idea that MeHg{sup +} is usually of biological origin in the marine environment. The concentration of

An ingenious strategy of preparing TiO2/g-C3N4 heterojunction photocatalyst: In situ growth of TiO2 nanocrystals on g-C3N4 nanosheets via impregnation-calcination method

Science.gov (United States)

Zhang, Guanghui; Zhang, Tianyong; Li, Bin; Jiang, Shuang; Zhang, Xia; Hai, Li; Chen, Xingwei; Wu, Wubin

2018-03-01

An ingenious method was employed to design and fabricate the TiO2/g-C3N4 heterojunction photocatalysts in this study. The thermal oxidation etching of g-C3N4 nanosheets and the in situ growth of TiO2 nanocrystal on the surface of g-C3N4 nanosheets were completed simultaneously by the calcination process. The g-C3N4 nanosheets played a crucial role in regulating and assembling the structures and morphologies of TiO2. Furthermore, the thickness and content of g-C3N4, and the crystallinity of TiO2 in TiO2/g-C3N4 composites could be regulated and controlled by the calcination temperature. Among the resultant TiO2/g-C3N4 samples, the TiO2/g-C3N4 sample with 41.6 wt% g-C3N4 exhibited the highest photocatalytic activity. It could degrade almost all MO molecules under visible light irradiation within 3 h. Moreover, it displayed higher visible light photocatalytic performance for degrading MO solution than pure g-C3N4 and D-TiO2. The synergistic effect between TiO2 and g-C3N4 makes significant contributions to the enhancement of the visible light photocatalytic activity. In addition, the favorable photocatalytic performance of TiO2/g-C3N4 nanocomposites is also attributed to the porous structures and uniform morphologies, and large surface area. Furthermore, the resultant TiO2/g-C3N4 exhibits excellent photocatalytic stability. Radical trapping experiments indicated that rad O2- and h+ were the main reactive species during the photodegradation process under visible light irradiation. Hopefully, the results can offer new design and strategy for preparing other g-C3N4-based nanocomposites for environmental and energy applications.

[Study on rapid analysis method of pesticide contamination in processed foods by GC-MS and GC-FPD].

Science.gov (United States)

Kobayashi, Maki; Otsuka, Kenji; Tamura, Yasuhiro; Tomizawa, Sanae; Kamijo, Kyoko; Iwakoshi, Keiko; Sato, Chizuko; Nagayama, Toshihiro; Takano, Ichiro

2011-01-01

A simple and rapid method using GC-MS and GC-FPD for the determination of pesticide contamination in processed food has been developed. Pesticides were extracted from a sample with ethyl acetate in the presence of anhydrous sodium sulfate, then cleaned up with a combination of mini-columns, such as macroporous diatomaceous earth, C18, GCB (graphite carbon black) and PSA. Recovery tests of 57 pesticides (known to be toxic or harmful) from ten kinds of processed foods (butter, cheese, corned beef, dried shrimp, frozen Chinese dumplings, grilled eels, instant noodles, kimchi, retort-packed curry and wine) were performed, and the recovery rates were mostly between 70% and 120%. This method can be used to judge whether or not processed foods are contaminated with pesticides at potentially harmful levels.

Existing and emerging technologies for measuring stable isotope labelled retinol in biological samples: isotope dilution analysis of body retinol stores.

Science.gov (United States)

Preston, Tom

2014-01-01

This paper discusses some of the recent improvements in instrumentation used for stable isotope tracer measurements in the context of measuring retinol stores, in vivo. Tracer costs, together with concerns that larger tracer doses may perturb the parameter under study, demand that ever more sensitive mass spectrometric techniques are developed. GCMS is the most widely used technique. It has high sensitivity in terms of sample amount and uses high resolution GC, yet its ability to detect low isotope ratios is limited by background noise. LCMSMS may become more accessible for tracer studies. Its ability to measure low level stable isotope tracers may prove superior to GCMS, but it is isotope ratio MS (IRMS) that has been designed specifically for low level stable isotope analysis through accurate analysis of tracer:tracee ratios (the tracee being the unlabelled species). Compound-specific isotope analysis, where GC is interfaced to IRMS, is gaining popularity. Here, individual 13C-labelled compounds are separated by GC, combusted to CO2 and transferred on-line for ratiometric analysis by IRMS at the ppm level. However, commercially-available 13C-labelled retinol tracers are 2 - 4 times more expensive than deuterated tracers. For 2H-labelled compounds, GC-pyrolysis-IRMS has now become more generally available as an operating mode on the same IRMS instrument. Here, individual compounds are separated by GC and pyrolysed to H2 at high temperature for analysis by IRMS. It is predicted that GC-pyrolysis-IRMS will facilitate low level tracer procedures to measure body retinol stores, as has been accomplished in the case of fatty acids and amino acids. Sample size requirements for GC-P-IRMS may exceed those of GCMS, but this paper discusses sample preparation procedures and predicts improvements, particularly in the efficiency of sample introduction.

Influence of sample temperature and environmental humidity on measurements of benzene in ambient air by transportable GC-PID

Directory of Open Access Journals (Sweden)

C. Romero-Trigueros

2017-10-01

Full Text Available Calibration of in situ analysers of air pollutants is usually done with dry standards. In this paper, the influence of sample temperature and environmental humidity on benzene measurements by gas chromatography coupled with a photoionisation detector (GC-PID is studied. Two reference gas mixtures (40 and 5 µg m−3 nominal concentration benzene in air were subjected to two temperature cycles (20/5/20 °C and 20/35/20 °C and measured with two identical GC-PIDs. The change in sample temperature did not produce any significant change in readings. Regarding ambient humidity, the chromatographs were calibrated for benzene with dry gases and subjected to measure reference standards with humidity (20 and 80 % at 20 °C. When measuring a concentration of 0.5 µg m−3 benzene in air, the levels of humidity tested did not produce any significant interference in measurements taken with any of the analysers. However, when measuring a concentration of 40 µg m−3, biases in measurements of 18 and 21 % for each respective analyser were obtained when the relative humidity of the sample was 80 % at 20 °C. Further tests were carried out to study the nature of this interference. Results show that humidity interference depends on both the amount fractions of water vapour and benzene. If benzene concentrations in an area are close to its annual limit value (5 µg m−3, biases of 2.2 % can be expected when the absolute humidity is 8.6 g cm−3 – corresponding to a relative humidity of 50 % at 20 °C. This can be accounted for in the uncertainty budget of measurements with no need for corrections. If benzene concentrations are above the annual limit value, biases become higher. Thus, in these cases, actions should be taken to reduce the humidity interference, as an underestimation of benzene concentrations may cause a mismanagement of air quality in these situations.

Magnetically Separable Fe2O3/g-C3N4 Nanocomposites with Cocoon-Like Shape: Magnetic Properties and Photocatalytic Activities

Science.gov (United States)

Yu, Xiaojia; Yang, Xiaoyu; Li, Guang

2018-01-01

We report magnetically separable Fe2O3/g-C3N4 nanocomposites as a photocatalyst under visible-light irradiation in this study. The Fe2O3/g-C3N4 nanocomposites were synthesized through a two-step hydrothermal method. The Fe2O3 with cocoon-like shape was obviously dispersed on the surface of g-C3N4 with porous and layered nanostructure as seen from micrographs of the particles. Furthermore, the magnetic conversion of the samples was studied via vibrating sample magnetometer technology. It was found that the saturated magnetization Ms of the Fe2O3/g-C3N4 nanoparticles obviously decreased in the presence of g-C3N4, and the photocatalytic activity of the samples investigated by degrading Rhodamine B suggested that the Fe2O3/g-C3N4 photocatalyst was prior to the pure Fe2O3 and g-C3N4 samples. In addition, the magnetically separable ability of Fe2O3/g-C3N4 nanocomposites was efficiently exhibited by an external magnet.

GC-Content Normalization for RNA-Seq Data

Science.gov (United States)

2011-01-01

Background Transcriptome sequencing (RNA-Seq) has become the assay of choice for high-throughput studies of gene expression. However, as is the case with microarrays, major technology-related artifacts and biases affect the resulting expression measures. Normalization is therefore essential to ensure accurate inference of expression levels and subsequent analyses thereof. Results We focus on biases related to GC-content and demonstrate the existence of strong sample-specific GC-content effects on RNA-Seq read counts, which can substantially bias differential expression analysis. We propose three simple within-lane gene-level GC-content normalization approaches and assess their performance on two different RNA-Seq datasets, involving different species and experimental designs. Our methods are compared to state-of-the-art normalization procedures in terms of bias and mean squared error for expression fold-change estimation and in terms of Type I error and p-value distributions for tests of differential expression. The exploratory data analysis and normalization methods proposed in this article are implemented in the open-source Bioconductor R package EDASeq. Conclusions Our within-lane normalization procedures, followed by between-lane normalization, reduce GC-content bias and lead to more accurate estimates of expression fold-changes and tests of differential expression. Such results are crucial for the biological interpretation of RNA-Seq experiments, where downstream analyses can be sensitive to the supplied lists of genes. PMID:22177264

High-throughput droplet analysis and multiplex DNA detection in the microfluidic platform equipped with a robust sample-introduction technique

International Nuclear Information System (INIS)

Chen, Jinyang; Ji, Xinghu; He, Zhike

2015-01-01

In this work, a simple, flexible and low-cost sample-introduction technique was developed and integrated with droplet platform. The sample-introduction strategy was realized based on connecting the components of positive pressure input device, sample container and microfluidic chip through the tygon tubing with homemade polydimethylsiloxane (PDMS) adaptor, so the sample was delivered into the microchip from the sample container under the driving of positive pressure. This sample-introduction technique is so robust and compatible that could be integrated with T-junction, flow-focus or valve-assisted droplet microchips. By choosing the PDMS adaptor with proper dimension, the microchip could be flexibly equipped with various types of familiar sample containers, makes the sampling more straightforward without trivial sample transfer or loading. And the convenient sample changing was easily achieved by positioning the adaptor from one sample container to another. Benefiting from the proposed technique, the time-dependent concentration gradient was generated and applied for quantum dot (QD)-based fluorescence barcoding within droplet chip. High-throughput droplet screening was preliminarily demonstrated through the investigation of the quenching efficiency of ruthenium complex to the fluorescence of QD. More importantly, multiplex DNA assay was successfully carried out in the integrated system, which shows the practicability and potentials in high-throughput biosensing. - Highlights: • A simple, robust and low-cost sample-introduction technique was developed. • Convenient and flexible sample changing was achieved in microfluidic system. • Novel strategy of concentration gradient generation was presented for barcoding. • High-throughput droplet screening could be realized in the integrated platform. • Multiplex DNA assay was successfully carried out in the droplet platform

High-throughput droplet analysis and multiplex DNA detection in the microfluidic platform equipped with a robust sample-introduction technique

Energy Technology Data Exchange (ETDEWEB)

Chen, Jinyang; Ji, Xinghu [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); He, Zhike, E-mail: zhkhe@whu.edu.cn [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Suzhou Institute of Wuhan University, Suzhou 215123 (China)

2015-08-12

In this work, a simple, flexible and low-cost sample-introduction technique was developed and integrated with droplet platform. The sample-introduction strategy was realized based on connecting the components of positive pressure input device, sample container and microfluidic chip through the tygon tubing with homemade polydimethylsiloxane (PDMS) adaptor, so the sample was delivered into the microchip from the sample container under the driving of positive pressure. This sample-introduction technique is so robust and compatible that could be integrated with T-junction, flow-focus or valve-assisted droplet microchips. By choosing the PDMS adaptor with proper dimension, the microchip could be flexibly equipped with various types of familiar sample containers, makes the sampling more straightforward without trivial sample transfer or loading. And the convenient sample changing was easily achieved by positioning the adaptor from one sample container to another. Benefiting from the proposed technique, the time-dependent concentration gradient was generated and applied for quantum dot (QD)-based fluorescence barcoding within droplet chip. High-throughput droplet screening was preliminarily demonstrated through the investigation of the quenching efficiency of ruthenium complex to the fluorescence of QD. More importantly, multiplex DNA assay was successfully carried out in the integrated system, which shows the practicability and potentials in high-throughput biosensing. - Highlights: • A simple, robust and low-cost sample-introduction technique was developed. • Convenient and flexible sample changing was achieved in microfluidic system. • Novel strategy of concentration gradient generation was presented for barcoding. • High-throughput droplet screening could be realized in the integrated platform. • Multiplex DNA assay was successfully carried out in the droplet platform.

Determination of selected organophosphorus pesticides using GC ...

African Journals Online (AJOL)

A reproducible analytical method utilising GC-MS is presented for the analysis of thirteen organophosphorus insecticides (OPs) often found in environmental aqueous samples. Extraction of filtered river and canal water (100 mL), fortified with the OPs, was conducted using solid-phase extraction and eluted with a variety of ...

Synthesis of 1-octacosanol and GC-C-IRMS discrimination of samples from different origin.

Science.gov (United States)

Cravotto, Giancarlo; Calcio Gaudino, Emanuela; Barge, Alessandro; Binello, Arianna; Albertino, Andrea; Aghemo, Costanza

2010-03-01

Lately, long-chain primary alcohols have been investigated in depth on account of their biological activities. In particular, 1-octacosanol (C(28)H(57)OH), the main component of policosanol, the hypolipidaemic fatty alcohol mixture obtained from sugar cane wax, has been the subject of a multitude of pharmacological studies. The aim of this work was to search a convenient synthetic protocol for the preparation of 1-octacosanol in a gram scale. The key step was a Wittig reaction between the octadecyltriphenylphosphonium ylide and the methyl 10-oxodecanoate. Some steps were further improved by power ultrasound and microwave irradiation, either alone or in combination. Our methodology is suitable for a rapid generation of homologues by varying the chain length in the alkyl halide. Due to the high commercial value, a series of 1-octacosanol samples, either isolated from natural sources or from synthesis (different origin and suppliers), were analysed by gas chromatography-combustion-isotopic ratio mass spectrometry (GC-C-IRMS) and according to the carbon isotopic content, classified on the basis of their origin.

Analysis of stable isotope assisted metabolomics data acquired by GC-MS

International Nuclear Information System (INIS)

Wei, Xiaoli; Shi, Biyun; Koo, Imhoi; Yin, Xinmin; Lorkiewicz, Pawel; Suhail, Hamid; Rattan, Ramandeep; Giri, Shailendra; McClain, Craig J.

2017-01-01

Stable isotope assisted metabolomics (SIAM) measures the abundance levels of metabolites in a particular pathway using stable isotope tracers (e.g., 13 C, 18 O and/or 15 N). We report a method termed signature ion approach for analysis of SIAM data acquired on a GC-MS system equipped with an electron ionization (EI) ion source. The signature ion is a fragment ion in EI mass spectrum of a derivatized metabolite that contains all atoms of the underivatized metabolite, except the hydrogen atoms lost during derivatization. In this approach, GC-MS data of metabolite standards were used to recognize the signature ion from the EI mass spectra acquired from stable isotope labeled samples, and a linear regression model was used to deconvolute the intensity of overlapping isotopologues. A mixture score function was also employed for cross-sample chromatographic peak list alignment to recognize the chromatographic peaks generated by the same metabolite in different samples, by simultaneously evaluating the similarity of retention time and EI mass spectrum of two chromatographic peaks. Analysis of a mixture of 16 13 C-labeled and 16 unlabeled amino acids showed that the signature ion approach accurately identified and quantified all isotopologues. Analysis of polar metabolite extracts from cells respectively fed with uniform 13 C-glucose and 13 C-glutamine further demonstrated that this method can also be used to analyze the complex data acquired from biological samples. - Highlights: • A signature ion approach is developed for analysis of stable isotope GC-MS data. • GC-MS data of compound standards are used for selection of the signature ion. • Linear regression model is used to deconvolute the overlapping isotopologue peaks. • The developed method was tested by known compounds and biological samples.

Determination of polycyclic aromatic hydrocarbons in deposited waste using GC-MSD. Bestimmung von polycyclischen aromatischen Kohlenwasserstoffen in Deponiegut mittels GC-MSD

Energy Technology Data Exchange (ETDEWEB)

Treffert, U. (chemlab, Gesellschaft fuer Analytik und Umweltberatung mbH, Bensheim (Germany). Abt. ' ' Organische Analytik' ' ); Kolb, M. (Fachhochschule Aalen (Germany)); Stoerk, H. (chemlab, Gesellschaft fuer Analytik und Umweltberatung mbH, Bensheim (Germany))

1999-06-01

The articel describes an analysis method for the determination of 16 polycyclic aromatic hydrocarbons in deposited waste. The single steps are described very detailed: sample preparation by extraction, evaporation, flash-chromatography (Al[sub 2]O[sub 3]), quantitative analysis by GC-MSD. (SR)

The measurement of muscle protein synthesis in broilers with a flooding dose technique: use of 15N-labelled phenylalanine, GC-MS and GC-C-IRMS.

Science.gov (United States)

Dänicke, S; Böttcher, W; Simon, O; Jeroch, H

2001-01-01

An experiment was carried out to measure fractional muscle protein synthesis rates (k(s)) in broilers with injection of a flooding dose of phenylalanine (1 ml/100 g body weight of 150 mM phenylalanine; 38 atom percent excess (APE) [15N]phenylalanine). K(s) was calculated from the [15N] enrichment in phenylalanine of tissue-free and protein-bound phenylalanine using both gas chromatography mass spectrometry (GC-MS) and gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS) for measurements after a 10 min isotope incorporation period. The tertiary-butyldimethylsilyl (t-BDMS) derivatives of phenylalanine were used for gas chromatographic separation in both systems. GC-MS and GC-C-IRMS were calibrated for a range of 7 to 37 [15N]APE and 0 to 0.62 [15N]APE, respectively, and for sample sizes of 0.45 to 4.5 nmol phenylalanine and 7 to 40 nmol phenylalanine, respectively. Reproducibility of standards as a measure of precision varied from 0.06 to 0.29 [15N]APE and from 0.0004 to 0.0018 [15N]APE in GC-MS and GC-C-IRMS, respectively. K(s) was measured in the m. pectoralis major of broilers fed rye based diets (56%) which were provided either unsupplemented (-) or supplemented (+) with an enzyme preparation containing xylanase. K(s) in breast muscles was significantly increased from 21.8%/d to 23.9%/d due to enzyme supplementation. It can be concluded from the study that the measurement of protein synthesis in broilers with the flooding dose technique can be carried out by using [15N]phenylalanine, GC-MS and GC-C-IRMS.

Development and Validation of a GC-FID Method for Diagnosis of Methylmalonic Acidemia

Directory of Open Access Journals (Sweden)

Fatemeh Keyfi

2016-05-01

Full Text Available Background: Urinary organic acids are water-soluble intermediates and end products of the metabolism of amino acids, carbohydrates, lipids, and a number of other metabolic processes. In the hereditary diseases known as organic acidurias, an enzyme or co-factor defect in a metabolic pathway leads to the accumulation and increased excretion of one or more of these acidic metabolites. Gas chromatography is the most commonly-used technology to separate and identify these metabolites. In this report the analytical conditions for the determination of methylmalonic acid using a gas chromatography/flame ionization detector (GC-FID are studied with the aim to establish a method to analyze organic acids in human urine. Methods: Studies included the GC-FID method development, the conditions of the derivatization (trimethylsilylation reaction, and the stability of the methylmalonic acid standard solution and trimethylsilyl derivatives during storage. Also, a systematic comparison between GC-FID and gas chromatography/mass spectrometry (GC-MS was performed. Results: The highest resolution and sensitivity were obtained at 60 oC with a 30 min reaction time. Standard solutions and derivatized samples were stable for 7 days at 4-8 oC. Relative standard deviations of within-day and day-to-day assay results were less than 5%. Methylmalonic acid was detected in thirty human urine samples by the proposed GC-FID, and the results were compared with gold standard technique GC-MS. The correlation coefficient between GC-MS and GC-FID was obtained with R2= 0.997. Conclusions: The developed method was applied to the quantitative analysis of methylmalonic acid in urine from hospitalized children with methylmalonic acidemia. With this method we aim to support pediatric clinics in Iran and assist in clinical diagnostics.

Immunotherapy of HIV-infected patients with Gc protein-derived macrophage activating factor (GcMAF).

Science.gov (United States)

Yamamoto, Nobuto; Ushijima, Naofumi; Koga, Yoshihiko

2009-01-01

Serum Gc protein (known as vitamin D3-binding protein) is the precursor for the principal macrophage activating factor (MAF). The MAF precursor activity of serum Gc protein of HIV-infected patients was lost or reduced because Gc protein is deglycosylated by alpha-N-acetylgalactosaminidase (Nagalase) secreted from HIV-infected cells. Therefore, macrophages of HIV-infected patients having deglycosylated Gc protein cannot be activated, leading to immunosuppression. Since Nagalase is the intrinsic component of the envelope protein gp120, serum Nagalase activity is the sum of enzyme activities carried by both HIV virions and envelope proteins. These Nagalase carriers were already complexed with anti-HIV immunoglobulin G (IgG) but retained Nagalase activity that is required for infectivity. Stepwise treatment of purified Gc protein with immobilized beta-galactosidase and sialidase generated the most potent macrophage activating factor (termed GcMAF), which produces no side effects in humans. Macrophages activated by administration of 100 ng GcMAF develop a large amount of Fc-receptors as well as an enormous variation of receptors that recognize IgG-bound and unbound HIV virions. Since latently HIV-infected cells are unstable and constantly release HIV virions, the activated macrophages rapidly intercept the released HIV virions to prevent reinfection resulting in exhaustion of infected cells. After less than 18 weekly administrations of 100 ng GcMAF for nonanemic patients, they exhibited low serum Nagalase activities equivalent to healthy controls, indicating eradication of HIV-infection, which was also confirmed by no infectious center formation by provirus inducing agent-treated patient PBMCs. No recurrence occurred and their healthy CD + cell counts were maintained for 7 years.

Constructing effective photocatalytic purification system with P-introduced g-C3N4 for elimination of UO22+

Science.gov (United States)

Wu, Xi; Jiang, Shujuan; Song, Shaoqing; Sun, Chuanzhi

2018-02-01

Due to the inherent defects of precursor molecular structure, the limited effect of structure in the formed g-C3N4 will weaken the extension of delocalization of π electrons between the adjacent tri-s-triazine or heptazine units of g-C3N4, which thus leads to poor visible-light absorption, low utilization efficiency of charge carrier. Herein, P-introduced g-C3N4 (PC3N4) photocatalysts were constructed by partially replacing C with tributyl phosphate as precursor, and the as-designed PC3N4 photocatalysts were used to eliminate aqueous uranyl ion by photocatalytic reduction technology under visible-light irradiation. Experimental and DFT revealed that introduction of P into g-C3N4 significantly modified its electronic structure, as reflected by the narrowed band gap, enhanced visible-light absorption as well as improved transfer capability of photogenerated charge. Therefore, photocatalytic activity of PC3N4 was much better than that of pristine g-C3N4 and conventional reducing-type photocatalysts. This study suggests an efficient strategy for construct effective visible-light-responsive photocatalysts for radioactive environmental remediation.

On-line Analysis of Catalytic Reaction Products Using a High-Pressure Tandem Micro-reactor GC/MS.

Science.gov (United States)

Watanabe, Atsushi; Kim, Young-Min; Hosaka, Akihiko; Watanabe, Chuichi; Teramae, Norio; Ohtani, Hajime; Kim, Seungdo; Park, Young-Kwon; Wang, Kaige; Freeman, Robert R

2017-01-01

When a GC/MS system is coupled with a pressurized reactor, the separation efficiency and the retention time are directly affected by the reactor pressure. To keep the GC column flow rate constant irrespective of the reaction pressure, a restrictor capillary tube and an open split interface are attached between the GC injection port and the head of a GC separation column. The capability of the attached modules is demonstrated for the on-line GC/MS analysis of catalytic reaction products of a bio-oil model sample (guaiacol), produced under a pressure of 1 to 3 MPa.

Linking the morphological and metabolomic response of Lactuca sativa L exposed to emerging contaminants using GC × GC-MS and chemometric tools.

Science.gov (United States)

Hurtado, Carlos; Parastar, Hadi; Matamoros, Víctor; Piña, Benjamín; Tauler, Romà; Bayona, Josep M

2017-07-26

The occurrence of contaminants of emerging concern (CECs) in irrigation waters (up to low μg L -1 ) and irrigated crops (ng g -1 in dry weight) has been reported, but the linkage between plant morphological changes and plant metabolomic response has not yet been addressed. In this study, a non-targeted metabolomic analysis was performed on lettuce (Lactuca sativa L) exposed to 11 CECs (pharmaceuticals, personal care products, anticorrosive agents and surfactants) by irrigation. The plants were watered with different CEC concentrations (0-50 µg L -1 ) for 34 days under controlled conditions and then harvested, extracted, derivatised and analysed by comprehensive two-dimensional gas chromatography coupled to a time-of-flight mass spectrometer (GC × GC-TOFMS). The resulting raw data were analysed using multivariate curve resolution (MCR) and partial least squares (PLS) methods. The metabolic response indicates that exposure to CECs at environmentally relevant concentrations (0.05 µg L -1 ) can cause significant metabolic alterations in plants (carbohydrate metabolism, the citric acid cycle, pentose phosphate pathway and glutathione pathway) linked to changes in morphological parameters (leaf height, stem width) and chlorophyll content.

Effect of the Gc-derived macrophage-activating factor precursor (preGcMAF) on phagocytic activation of mouse peritoneal macrophages.

Science.gov (United States)

Uto, Yoshihiro; Yamamoto, Syota; Takeuchi, Ryota; Nakagawa, Yoshinori; Hirota, Keiji; Terada, Hiroshi; Onizuka, Shinya; Nakata, Eiji; Hori, Hitoshi

2011-07-01

The 1f1f subtype of the Gc protein (Gc(1f1f) protein) was converted into Gc-derived macrophage-activating factor (GcMAF) by enzymatic processing in the presence of β-galactosidase of an activated B-cell and sialidase of a T-cell. We hypothesized that preGc(1f1f)MAF, the only Gc(1f1f) protein lacking galactose, can be converted to GcMAF in vivo because sialic acid is cleaved by residual sialidase. Hence, we investigated the effect of preGc(1f1f)MAF on the phagocytic activation of mouse peritoneal macrophages. We examined the sugar moiety of preGc(1f1f)MAF with a Western blot using peanut agglutinin (PNA) and Helix pomatia agglutinin (HPA) lectin. We also found that preGc(1f1f)MAF significantly enhanced phagocytic activity in mouse peritoneal macrophages but only in the presence of the mouse peritoneal fluid; the level of phagocytic activity was the same as that observed for GcMAF. PreGc(1f1f)MAF can be used as an effective macrophage activator in vivo.

Headspace solid-phase microextraction-gas chromatographic-time-of-flight mass spectrometric methodology for geographical origin verification of coffee

International Nuclear Information System (INIS)

Risticevic, Sanja; Carasek, Eduardo; Pawliszyn, Janusz

2008-01-01

Increasing consumer awareness of food safety issues requires the development of highly sophisticated techniques for the authentication of food commodities. The food products targeted for falsification are either products of high commercial value or those produced in large quantities. For this reason, the present investigation is directed towards the characterization of coffee samples according to the geographical origin. The conducted research involves the development of a rapid headspace solid-phase microextraction (HS-SPME)-gas chromatography-time-of-flight mass spectrometry (GC-TOFMS) method that is utilized for the verification of geographical origin traceability of coffee samples. As opposed to the utilization of traditional univariate optimization methods, the current study employs the application of multivariate experimental designs to the optimization of extraction-influencing parameters. Hence, the two-level full factorial first-order design aided in the identification of two influential variables: extraction time and sample temperature. The optimum set of conditions for the two variables was 12 min and 55 deg. C, respectively, as directed by utilization of Doehlert matrix and response surface methodology. The high-throughput automated SPME procedure was completed by implementing a single divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) 50/30 μm metal fiber with excellent durability properties ensuring the completion of overall sequence of coffee samples. The utilization of high-speed TOFMS instrument ensured the completion of one GC-MS run of a complex coffee sample in 7.9 min and the complete list of benefits provided by ChromaTOF software including fully automated background subtraction, baseline correction, peak find and mass spectral deconvolution algorithms was exploited during the data evaluation procedure. The combination of the retention index (RI) system using C 8 -C 40 alkanes and the mass spectral library search was utilized for the

Headspace solid-phase microextraction-gas chromatographic-time-of-flight mass spectrometric methodology for geographical origin verification of coffee

Energy Technology Data Exchange (ETDEWEB)

Risticevic, Sanja [Department of Chemistry, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L 3G1 (Canada); Carasek, Eduardo [Department of Chemistry, Federal University of Santa Catarina, Trindade, Florianopolis, 88040-900, Santa Catarina (Brazil); Pawliszyn, Janusz [Department of Chemistry, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L 3G1 (Canada)], E-mail: janusz@uwaterloo.ca

2008-06-09

Increasing consumer awareness of food safety issues requires the development of highly sophisticated techniques for the authentication of food commodities. The food products targeted for falsification are either products of high commercial value or those produced in large quantities. For this reason, the present investigation is directed towards the characterization of coffee samples according to the geographical origin. The conducted research involves the development of a rapid headspace solid-phase microextraction (HS-SPME)-gas chromatography-time-of-flight mass spectrometry (GC-TOFMS) method that is utilized for the verification of geographical origin traceability of coffee samples. As opposed to the utilization of traditional univariate optimization methods, the current study employs the application of multivariate experimental designs to the optimization of extraction-influencing parameters. Hence, the two-level full factorial first-order design aided in the identification of two influential variables: extraction time and sample temperature. The optimum set of conditions for the two variables was 12 min and 55 deg. C, respectively, as directed by utilization of Doehlert matrix and response surface methodology. The high-throughput automated SPME procedure was completed by implementing a single divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) 50/30 {mu}m metal fiber with excellent durability properties ensuring the completion of overall sequence of coffee samples. The utilization of high-speed TOFMS instrument ensured the completion of one GC-MS run of a complex coffee sample in 7.9 min and the complete list of benefits provided by ChromaTOF software including fully automated background subtraction, baseline correction, peak find and mass spectral deconvolution algorithms was exploited during the data evaluation procedure. The combination of the retention index (RI) system using C{sub 8}-C{sub 40} alkanes and the mass spectral library search was

Sampling and Analytical Method for Alpha-Dicarbonyl Flavoring Compounds via Derivatization with o-Phenylenediamine and Analysis Using GC-NPD

Directory of Open Access Journals (Sweden)

Stephanie M. Pendergrass

2016-01-01

Full Text Available A novel methodology is described for the sampling and analysis of diacetyl, 2,3-pentanedione, 2,3-hexanedione, and 2,3-heptanedione. These analytes were collected on o-phenylenediamine-treated silica gel tubes and quantitatively recovered as the corresponding quinoxaline derivatives. After derivatization, the sorbent was desorbed in 3 mL of ethanol solvent and analyzed using gas chromatography/nitrogen-phosphorous detection (GC/NPD. The limits of detection (LOD achieved for each analyte were determined to be in the range of 5–10 nanograms/sample. Evaluation of the on-tube derivatization procedure indicated that it is unaffected by humidities ranging from 20% to 80% and that the derivatization procedure was quantitative for analyte concentrations ranging from 0.1 μg to approximately 500 μg per sample. Storage stability studies indicated that the derivatives were stable for 30 days when stored at both ambient and refrigerated temperatures. Additional studies showed that the quinoxaline derivatives were quantitatively recovered when sampling up to a total volume of 72 L at a sampling rate of 50 cc/min. This method will be important to evaluate and monitor worker exposures in the food and flavoring industry. Samples can be collected over an 8-hour shift with up to 288 L total volume collected regardless of time, sampling rate, and/or the effects of humidity.

Determinação de compostos nitrogenados aromáticos em alcatrão de carvão através da cromatografia gasosa bidimensional abrangente acoplada à espectrometria de massas

OpenAIRE

Juliana Macedo da Silva

2014-01-01

A cromatografia gasosa bidimensional abrangente (GC×GC) é uma excelente técnica analítica para a determinação de diversos compostos em matrizes complexas, como é o caso do alcatrão de carvão, objeto deste estudo. O alcatrão foi obtido através do processo de pirólise e submetido à análise por GC×GC visando a especiação de compostos nitrogenados aromáticos. A GC×GC acoplada à espectrometria de massas com analisadores do tipo quadrupolar (qMS) e por tempo de voo (TOFMS) foram utilizados para a d...

Surfactant assisted pulsed two-phase electromembrane extraction followed by GC analysis for quantification of basic drugs in biological samples.

Science.gov (United States)

Zahedi, Pegah; Davarani, Saied Saeed Hosseiny; Moazami, Hamid Reza; Nojavan, Saeed

2016-01-05

In this work, a simple and efficient surfactant assisted pulsed two-phase electromembrane extraction (SA-PEME) procedure combined with gas chromatography (GC) has been developed for the determination of alfentanil, sufentanil and methadone in various samples. It has been found that the addition of anionic surfactant causes the accumulation of the cationic analytes at the SLM/solution interface resulting in an easier transfer of the analytes into the organic phase. The method was accomplished with 1-octanol as the acceptor phase and supported liquid membrane (SLM) by means of an 80 V pulsed electrical driving force and the extraction time of 20 min. The model analytes were extracted from 3.0 mL sample solution (pH 4.0) containing 0.02% w/v surfactant (sodium dodecyl sulfate). The duty cycle of 92% and frequency of 0.357 Hz gave the best performance. Extraction recoveries in the range of 70.5-95.2% and satisfactory repeatability (7.6samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Intra-genomic GC heterogeneity in sauropsids: evolutionary insights from cDNA mapping and GC3 profiling in snake

Science.gov (United States)

2012-01-01

Background Extant sauropsids (reptiles and birds) are divided into two major lineages, the lineage of Testudines (turtles) and Archosauria (crocodilians and birds) and the lineage of Lepidosauria (tuatara, lizards, worm lizards and snakes). Karyotypes of these sauropsidan groups generally consist of macrochromosomes and microchromosomes. In chicken, microchromosomes exhibit a higher GC-content than macrochromosomes. To examine the pattern of intra-genomic GC heterogeneity in lepidosaurian genomes, we constructed a cytogenetic map of the Japanese four-striped rat snake (Elaphe quadrivirgata) with 183 cDNA clones by fluorescence in situ hybridization, and examined the correlation between the GC-content of exonic third codon positions (GC3) of the genes and the size of chromosomes on which the genes were localized. Results Although GC3 distribution of snake genes was relatively homogeneous compared with those of the other amniotes, microchromosomal genes showed significantly higher GC3 than macrochromosomal genes as in chicken. Our snake cytogenetic map also identified several conserved segments between the snake macrochromosomes and the chicken microchromosomes. Cross-species comparisons revealed that GC3 of most snake orthologs in such macrochromosomal segments were GC-poor (GC3 < 50%) whereas those of chicken orthologs in microchromosomes were relatively GC-rich (GC3 ≥ 50%). Conclusion Our results suggest that the chromosome size-dependent GC heterogeneity had already occurred before the lepidosaur-archosaur split, 275 million years ago. This character was probably present in the common ancestor of lepidosaurs and but lost in the lineage leading to Anolis during the diversification of lepidosaurs. We also identified several genes whose GC-content might have been influenced by the size of the chromosomes on which they were harbored over the course of sauropsid evolution. PMID:23140509

Introduction to suspended-sediment sampling

Science.gov (United States)

Nolan, K. Michael; Gray, John R.; Glysson, G. Douglas

2005-01-01

Knowledge of the amount and timing of sediment transport in streams is important to those directly or indirectly responsible for developing and managing water and land resources. Such data are often used to judge the health of watershed and the success or failure of activities designed to mitigate adverse impacts of sediment on streams and stream habitats. This training class presents an introduction to methods currently used by the U.S. Geological Survey (USGS) to sample suspended-sediment concentrations in streams. The presentation is narrated, but you control the pace of the presentation. If the computer you are using can view 'MPEG' videos you will be able to take advantage of videos interspersed in the presentation. A test, found at the end of the presentation, can be taken to assess how well you understood the training material. The class, which is registered as class SW4416 with the National Training Center of the USGS, should take two or three hours to complete. In order to use the presentation provided via this Web page, you will need to download a large disc images (linked below) and 'burn' it to a blank CD-ROM using a CD-ROM recorder on your computer. The presentation will only run on a Windows-based personal computer (PC). The presentation was developed using Macromedia Director MX 20041 and is contained in the file 'SIR05-5077.exe' which should autolaunch. If it does not, the presentation can be started by double-clicking on the file name. A sound card and speakers are necessary to take advantage of narrations that accompany the presentation. Text of narrations is provided, if you are unable to listen to narrations. Instructions for installing and running the presentation are included in the file 'Tutorial.htm', which is on the CD. 1 Registered Trademark: Macromedia Incorporated

Use of the Keele injector for sample introduction for gas chromatographic analysis of vinclozolin in lettuces.

Science.gov (United States)

Shim, J H; Lee, Y S; Kim, M R; Lee, C J; Kim, I S

2003-10-10

We examined a Keele injector for sample introduction for gas chromatographic analysis of vinclozolin treated in lettuces. Samples in milligram quantity were introduced into a glass tube in a Keele injector at a gas chromatograph injection port. The glass tube was then crushed to allow the sample to carry onto a capillary column in a normal manner. The standard calibration curve for quantitative detection of vinclozolin was obtained by determining vinclozolin spiked in samples at variable concentrations. The calibration curve showed a linear response to vinclozolin ranging from 0.05 to 1.0 microg/g, giving a slope value of 174.8, the y-intercept value of -2.8146 and the mean r2-value of 0.9994. Limit of quantification for vinclozolin was 0.05 microg/g by this method, comparable to 0.01 microg/g by a normal injector. When samples treated previously with vinclozolin were determined by the Keele injector, vinclozolin was found to be about 30% lower as compared to a normal method, suggesting about 70% recovery of the spiked vinclozolin by the Keele injector. From these results, the Keele injector was suggested to be potential for sample introduction in gas chromatographic analysis of vinclozolin in lettuce samples.

Evaluation of a gas chromatograph with a novel surface acoustic wave detector (SAW GC) for screening of volatile organic compounds in Hanford waste tank samples

International Nuclear Information System (INIS)

Lockrem, L.L.

1998-01-01

A novel instrument, a gas chromatograph with a Surface Acoustic Wave Detector (SAW GC), was evaluated for the screening of organic compounds in Hanford tank headspace vapors. Calibration data were developed for the most common organic compounds, and the accuracy and precision were measured with a certified standard. The instrument was tested with headspace samples collected from seven Hanford waste tanks

Rapid Quantification of N-Methyl-2-pyrrolidone in Polymer Matrices by Thermal Desorption-GC/MS.

Science.gov (United States)

Kim, Young-Min; Kim, Jae Woo; Moon, Hye Mi; Lee, Min-Jin; Hosaka, Akihiko; Watanabe, Atsushi; Teramae, Norio; Park, Young-Kwon; Myung, Seung-Woon

2017-01-01

Analysis of a residual solvent in polymeric materials has become an important issue due to the increased regulations and standards for its use. N-Methyl-2-pyrrolidone (NMP) is a solvent widely used in many industries and restricted as one of the chemicals under EU REACH regulations due to its potential harmful effects. In this study, thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) is applied for the quantitative analysis of NMP with the use of a polymer-coated sample cup. By using the polymer-coated sample cup, the vaporization of NMP was prevented during waiting time before TD-GC/MS analysis. The calibration curve for the TD method showed good linearity (correlation coefficient, r 2 = 0.9998) and precision values (below 5.3% RSD). NMP recovery rates in different polymer matrices (PS, PMMA and PVC) were in the range of 98.8 to 106.6% with RSD values below 5.0%. The quantification result (600 mg NMP/kg PVC) for the blind NMP carrying sample in a PVC matrix by TD-GC/MS was higher than that (532 mg NMP/kg PVC) by solvent extraction-GC/MS method.

Comparison of the decomposition VOC profile during winter and summer in a moist, mid-latitude (Cfb climate.

Directory of Open Access Journals (Sweden)

Shari L Forbes

Full Text Available The investigation of volatile organic compounds (VOCs associated with decomposition is an emerging field in forensic taphonomy due to their importance in locating human remains using biological detectors such as insects and canines. A consistent decomposition VOC profile has not yet been elucidated due to the intrinsic impact of the environment on the decomposition process in different climatic zones. The study of decomposition VOCs has typically occurred during the warmer months to enable chemical profiling of all decomposition stages. The present study investigated the decomposition VOC profile in air during both warmer and cooler months in a moist, mid-latitude (Cfb climate as decomposition occurs year-round in this environment. Pig carcasses (Sus scrofa domesticus L. were placed on a soil surface to decompose naturally and their VOC profile was monitored during the winter and summer months. Corresponding control sites were also monitored to determine the natural VOC profile of the surrounding soil and vegetation. VOC samples were collected onto sorbent tubes and analyzed using comprehensive two-dimensional gas chromatography--time-of-flight mass spectrometry (GC × GC-TOFMS. The summer months were characterized by higher temperatures and solar radiation, greater rainfall accumulation, and comparable humidity when compared to the winter months. The rate of decomposition was faster and the number and abundance of VOCs was proportionally higher in summer. However, a similar trend was observed in winter and summer demonstrating a rapid increase in VOC abundance during active decay with a second increase in abundance occurring later in the decomposition process. Sulfur-containing compounds, alcohols and ketones represented the most abundant classes of compounds in both seasons, although almost all 10 compound classes identified contributed to discriminating the stages of decomposition throughout both seasons. The advantages of GC × GC-TOFMS were

AUTOMATED ANALYSIS OF AQUEOUS SAMPLES CONTAINING PESTICIDES, ACIDIC/BASIC/NEUTRAL SEMIVOLATILES AND VOLATILE ORGANIC COMPOUNDS BY SOLID PHASE EXTRACTION COUPLED IN-LINE TO LARGE VOLUME INJECTION GC/MS

Science.gov (United States)

Data is presented on the development of a new automated system combining solid phase extraction (SPE) with GC/MS spectrometry for the single-run analysis of water samples containing a broad range of organic compounds. The system uses commercially available automated in-line 10-m...

Mutational Biases and GC-Biased Gene Conversion Affect GC Content in the Plastomes of Dendrobium Genus

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Zhitao Niu

2017-11-01

Full Text Available The variation of GC content is a key genome feature because it is associated with fundamental elements of genome organization. However, the reason for this variation is still an open question. Different kinds of hypotheses have been proposed to explain the variation of GC content during genome evolution. However, these hypotheses have not been explicitly investigated in whole plastome sequences. Dendrobium is one of the largest genera in the orchid species. Evolutionary studies of the plastomic organization and base composition are limited in this genus. In this study, we obtained the high-quality plastome sequences of D. loddigesii and D. devonianum. The comparison results showed a nearly identical organization in Dendrobium plastomes, indicating that the plastomic organization is highly conserved in Dendrobium genus. Furthermore, the impact of three evolutionary forces—selection, mutational biases, and GC-biased gene conversion (gBGC—on the variation of GC content in Dendrobium plastomes was evaluated. Our results revealed: (1 consistent GC content evolution trends and mutational biases in single-copy (SC and inverted repeats (IRs regions; and (2 that gBGC has influenced the plastome-wide GC content evolution. These results suggest that both mutational biases and gBGC affect GC content in the plastomes of Dendrobium genus.

Mutational Biases and GC-Biased Gene Conversion Affect GC Content in the Plastomes of Dendrobium Genus

Science.gov (United States)

Niu, Zhitao; Xue, Qingyun; Wang, Hui; Xie, Xuezhu; Zhu, Shuying; Liu, Wei; Ding, Xiaoyu

2017-01-01

The variation of GC content is a key genome feature because it is associated with fundamental elements of genome organization. However, the reason for this variation is still an open question. Different kinds of hypotheses have been proposed to explain the variation of GC content during genome evolution. However, these hypotheses have not been explicitly investigated in whole plastome sequences. Dendrobium is one of the largest genera in the orchid species. Evolutionary studies of the plastomic organization and base composition are limited in this genus. In this study, we obtained the high-quality plastome sequences of D. loddigesii and D. devonianum. The comparison results showed a nearly identical organization in Dendrobium plastomes, indicating that the plastomic organization is highly conserved in Dendrobium genus. Furthermore, the impact of three evolutionary forces—selection, mutational biases, and GC-biased gene conversion (gBGC)—on the variation of GC content in Dendrobium plastomes was evaluated. Our results revealed: (1) consistent GC content evolution trends and mutational biases in single-copy (SC) and inverted repeats (IRs) regions; and (2) that gBGC has influenced the plastome-wide GC content evolution. These results suggest that both mutational biases and gBGC affect GC content in the plastomes of Dendrobium genus. PMID:29099062

Association between VEGF polymorphisms (936c/t, -460t/c and -634g/c) with haplotypes and coronary heart disease susceptibility.

Science.gov (United States)

Han, Xia; Liu, Lili; Niu, Jiamin; Yang, Jun; Zhang, Zengtang; Zhang, Zhiqiang

2015-01-01

Our aim was to investigate the association between single nucleotide polymorphisms (SNPs) of vascular endothelial growth factor (VEGF) and coronary heart disease (CHD) susceptibility in Chinese Han population. 144 CHD patients and 150 healthy individuals were enrolled in the study. Three SNPs (936C/T, -460T/C and -634G/C) of VEGF were chose and then were genotyped with Sequenom time-of-flight mass spectrometry (TOFMS). Odds ratio (OR) with 95% confidence interval (CI) were used to evaluate the association of genotypes and haplotypes and CHD susceptibility. The frequencies of -460T/C CC genotype (13.6%) was found higher in the case group than that of control group (6.7%), which indicated that CC genotype was a risk factor for CHD (OR=2.50, 95% CI=1.10-5.68). Correspondently, the C allele appeared to increase the risk of CHD (OR=1.54, 95% CI=1.07-2.22). For -634G/C polymorphism, the risk of the CC genotype carrier for CHD increased 2.24 fold compared to the wild genotype. Moreover, -634G/CC allele was significantly associated with CHD susceptibility (OR=1.65, 95% CI=1.15-2.36). In addition, +936C/T CT genotype and C allele appeared to be a genetic-susceptibility factors for CHD (OR=2.43, 95% CI=1.44-4.10; OR=1.95, 95% CI=1.26-3.02). The haplotype analysis showed that T-C-T, C-C-C and C-G-C haplotypes all could increase the risk for CHD (OR: 2.43, 2.77 and 2.33). we concluded VEGF polymorphisms were associated with CHD susceptibility. Moreover, the haplotypes of T-C-T, C-C-C and C-G-C all could increase the risk for CHD.

THE IDENTIFICATION OF THE BINDING MEDIA IN THE TANG DYNASTY CHINESE WALL PAINTINGS BY USING Py-GC/MS AND GC/MS TECHNIQUES

Directory of Open Access Journals (Sweden)

Hong GUO

2011-06-01

Full Text Available The archaeological discoveries of Tang tomb murals in Xi’an, China brought to light unprecedented data for the study of the art of the Tang Dynasty (618-907 AD. The spectacular murals with their particular contents provided first-hand material for the study of Chinese history and the techniques of wall paintings during the Tang Dynasty. In order to gain a better understanding of the materials used and to preserve those paintings, pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS and gas chromatography-mass spectrometry (GC/MS were applied for the characterization of the binding media in the paintings. The combination of these analytical techniques is an ideal methodology to identify binding media in unknown samples.

β-Galactosidase treatment is a common first-stage modification of the three major subtypes of Gc protein to GcMAF.

Science.gov (United States)

Uto, Yoshihiro; Yamamoto, Syota; Mukai, Hirotaka; Ishiyama, Noriko; Takeuchi, Ryota; Nakagawa, Yoshinori; Hirota, Keiji; Terada, Hiroshi; Onizuka, Shinya; Hori, Hitoshi

2012-06-01

The 1f1f subtype of the group-specific component (Gc) protein is converted into Gc protein-derived macrophage-activating factor (GcMAF) by enzymatic processing with β-galactosidase and sialidase. We previously demonstrated that preGc(1f1f)MAF, a full Gc(1f1f) protein otherwise lacking a galactosyl moiety, can be converted to GcMAF by treatment with mouse peritoneal fluid. Here, we investigated the effects of the β-galactosidase-treated 1s1s and 22 subtypes of Gc protein (preGc(1s1s)MAF and preGc₂₂MAF) on the phagocytic activation of mouse peritoneal macrophages. We demonstrated the presence of Gal-GalNAc disaccharide sugar structures in the Gc(1s1s) protein by western blotting using peanut agglutinin and Helix pomatia agglutinin lectin. We also found that preGc(1s1s)MAF and preGc₂₂MAF significantly enhanced the phagocytic activity of mouse peritoneal macrophages in the presence and absence of mouse peritoneal fluid. We demonstrate that preGc(1s1s)MAF and preGc₂₂MAF proteins can be used as effective macrophage activators.

Admission levels of serum Gc-globulin

DEFF Research Database (Denmark)

Schiødt, F V; Bondesen, S; Petersen, I

1996-01-01

Gc-globulin scavenges actin released from necrotic hepatocytes to the extracellular space. In 77 patients with fulminant hepatic failure (FHF) (excluding patients treated with liver transplantation), admission levels of serum Gc-globulin and degree of complexing with monomeric actin (complex ratio...... in the same range as the KCH criteria. An advantage of Gc-globulin is that it gives an estimate of the outcome already on admission. Acute liver transplantation should be considered in FHF patients with Gc-globulin less than 100 mg/L....

Introduction to generalized linear models

CERN Document Server

Dobson, Annette J

2008-01-01

Introduction Background Scope Notation Distributions Related to the Normal Distribution Quadratic Forms Estimation Model Fitting Introduction Examples Some Principles of Statistical Modeling Notation and Coding for Explanatory Variables Exponential Family and Generalized Linear Models Introduction Exponential Family of Distributions Properties of Distributions in the Exponential Family Generalized Linear Models Examples Estimation Introduction Example: Failure Times for Pressure Vessels Maximum Likelihood Estimation Poisson Regression Example Inference Introduction Sampling Distribution for Score Statistics Taylor Series Approximations Sampling Distribution for MLEs Log-Likelihood Ratio Statistic Sampling Distribution for the Deviance Hypothesis Testing Normal Linear Models Introduction Basic Results Multiple Linear Regression Analysis of Variance Analysis of Covariance General Linear Models Binary Variables and Logistic Regression Probability Distributions ...

Depth-profile analysis of thermoelectric layers on Si wafers by pulsed r.f. glow discharge time-of-flight mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Reinsberg, K.-G. [Institute for Inorganic and Applied Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, D-20146 Hamburg (Germany); Schumacher, C. [Institute for Applied Physics, University of Hamburg, Jungiusstrasse 11, D-20355 Hamburg (Germany); Tempez, A. [HORIBA Jobin Yvon, 16-18 rue du Canal, F-91160 Longjumeau (France); Nielsch, K. [Institute for Applied Physics, University of Hamburg, Jungiusstrasse 11, D-20355 Hamburg (Germany); Broekaert, J.A.C., E-mail: jose.broekaert@chemie.uni-hamburg.de [Institute for Inorganic and Applied Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, D-20146 Hamburg (Germany)

2012-10-15

In this work the depth-profile analysis of thermoelectric layers deposited on Au and Cr covered Si wafers with the aid of pulsed radiofrequency glow discharge time-of-flight mass spectrometry (pulsed RF-GD-TOFMS also called plasma profiling TOFMS (PP-TOFMS Trade-Mark-Sign )) is described. For thermoelectric materials the depth resolutions obtained with both PP-TOFMS and secondary ion mass spectrometry (SIMS) are shown to be well comparable and in the order of the roughness of the corresponding layers (between 20 and 3700 nm). With both methods a direct solid analysis without any preparation steps is possible. In addition, the analysis of the samples with PP-TOFMS proved to be faster by a factor of 26 compared to SIMS, as sputtering rates were found to be 80 nm s{sup -1} and 3 nm s{sup -1}, respectively. For the analyzed samples the results of PP-TOFMS and SIMS show that a homogeneous deposition was obtained. Quantitative results for all samples could also be obtained directly by PP-TOFMS when the stoichiometry of one sample was determined beforehand for instance by inductively coupled plasma optical emission spectrometry (ICP-OES) and scanning electron microscopy energy dispersive X-ray fluorescence spectrometry (SEM-EDX). For Bi{sub 2}Te{sub 3} the standard deviation for the main component concentrations within one sample then is found to be between 1.1% and 1.9% and it is 3.6% from sample to sample. For Sb{sub 2}Te{sub 3} the values within one sample are from 1.7% to 4.2% and from sample to sample 5.3%, respectively. - Highlights: Black-Right-Pointing-Pointer Depth resolution in sub micrometer size by glow discharge mass spectrometry. Black-Right-Pointing-Pointer Bi and Sb telluride layers composition with GD-TOF-MS, ICP-OES and SEM-EDX agree. Black-Right-Pointing-Pointer Homogeneities of layers measured with GD-TOF-MS and SIMS agree.

Separation of fatty acid methyl esters by GC-online hydrogenation × GC.

Science.gov (United States)

Delmonte, Pierluigi; Fardin-Kia, Ali Reza; Rader, Jeanne I

2013-02-05

The separation of fatty acid methyl esters (FAME) provided by a 200 m × 0.25 mm SLB-IL111 capillary column is enhanced by adding a second dimension of separation ((2)D) in a GC × GC design. Rather than employing two GC columns of different polarities or using different elution temperatures, the separation in the two-dimensional space is achieved by altering the chemical structure of selected analytes between the two dimensions of separation. A capillary tube coated with palladium is added between the first dimension of separation ((1)D) column and the cryogenic modulator, providing the reduction of unsaturated FAMEs to their fully saturated forms. The (2)D separation is achieved using a 2.5 m × 0.10 mm SLB-IL111 capillary column and separates FAMEs based solely on their carbon skeleton. The two-dimensional separation can be easily interpreted based on the principle that all the saturated FAMEs lie on a straight diagonal line bisecting the separation plane, while the FAMEs with the same carbon skeleton but differing in the number, geometric configuration or position of double bonds lie on lines parallel to the (1)D time axis. This technique allows the separation of trans fatty acids (FAs) and polyunsaturated FAs (PUFAs) in a single experiment and eliminates the overlap between PUFAs with different chain lengths. To our knowledge, this the first example of GC × GC in which a chemical change is instituted between the two dimensions to alter the relative retentions of components and identify unsaturated FAMEs.

Integrated multidimensional and comprehensive 2D GC analysis of fatty acid methyl esters.

Science.gov (United States)

Zeng, Annie Xu; Chin, Sung-Tong; Marriott, Philip J

2013-03-01

Fatty acid methyl ester (FAME) profiling in complex fish oil and milk fat samples was studied using integrated comprehensive 2D GC (GC × GC) and multidimensional GC (MDGC). Using GC × GC, FAME compounds--cis- and trans-isomers, and essential fatty acid isomers--ranging from C18 to C22 in fish oil and C18 in milk fat were clearly displayed in contour plot format according to structural properties and patterns, further identified based on authentic standards. Incompletely resolved regions were subjected to MDGC, with Cn (n = 18, 20) zones transferred to a (2)D column. Elution behavior of C18 FAME on various (2)D column phases (ionic liquids IL111, IL100, IL76, and modified PEG) was evaluated. Individual isolated Cn zones demonstrated about four-fold increased peak capacities. The IL100 provided superior separation, good peak shape, and utilization of elution space. For milk fat-derived FAME, the (2)D chromatogram revealed at least three peaks corresponding to C18:1, more than six peaks for cis/trans-C18:2 isomers, and two peaks for C18:3. More than 17 peaks were obtained for the C20 region of fish oil-derived FAMEs using MDGC, compared with ten peaks using GC × GC. The MDGC strategy is useful for improved FAME isomer separation and confirmation. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improving g-C3N4 photocatalysis for NOx removal by Ag nanoparticles decoration

International Nuclear Information System (INIS)

Sun, Yanjuan; Xiong, Ting; Ni, Zilin; Liu, Jie; Dong, Fan; Zhang, Wei; Ho, Wing-Kei

2015-01-01

Graphical abstract: Ag/g-C 3 N 4 nanocomposites were prepared via a facile method for enhanced photocatalytic NO x removal due to surface plasmon resonance of Ag. - Highlights: • The Ag/g-C 3 N 4 nanocomposites were prepared using urea as the precursor. • The Ag/g-C 3 N 4 nanocomposites were applied in removal of NO x in air. • The Ag nanoparticles enhanced the photocatalytic activity of g-C 3 N 4 . • The surface plasmon resonance of Ag played a key role in photocatalysis. - Abstract: In order to overcome the intrinsic drawback of pristine g-C 3 N 4 , we prepared g-C 3 N 4 nanosheets with enhanced photocatalytic performance by Ag nanoparticles decoration using urea as the precursor. It was revealed that the monodispersed Ag nanoparticles were deposited on the surface of g-C 3 N 4 nanosheets. The Ag/g-C 3 N 4 nanocomposites were applied in removal of NO x in air under visible light irradiation. The results showed that the decoration of Ag nanoparticles not only enhanced the photocatalytic activity of g-C 3 N 4 nanosheets, but also benefited the oxidation of NO to final products. The increased visible light absorption arising from the surface plasmon resonance of Ag and improved separation and transfer of photoinduced carriers over Ag/g-C 3 N 4 composites were demonstrated by the UV–vis diffuse reflectance spectra and photoluminescence spectra, respectively. It was therefore proposed that the enhanced photocatalytic activity of Ag/g-C 3 N 4 composites could be attributed to the extended light response range and enhanced charge separation due to the introduction of Ag nanoparticles.

Determination of Organophosphorous Pesticides in Environmental Water Samples Using Surface-Engineered C18 Functionalized Silica-Coated Core-Shell Magnetic Nanoparticles-Based Extraction Coupled with GC-MS/MS Analysis.

Science.gov (United States)

Srivastava, Neha; Kumari, Supriya; Nair, Kishore; Alam, Samsul; Raza, Syed K

2017-05-01

The present paper depicts a novel method based on magnetic SPE (MSPE) for the determination of organophosphorus pesticides (OPs) such as phorate, malathion, and chlorpyrifos in environmental water samples. In this study, C18 functionalized silica-coated core-shell iron oxide magnetic nanoparticles (MNPs) were used as a surface-engineered magnetic sorbent for the selective extraction of pesticides from aqueous samples, followed by GC-MS and GC-tandem MS analysis for confirmative determination of the analytes. Various important method parameters, including quantity of MNP adsorbent, volume of sample, effective time for extraction, nature of the desorbing solvent, and pH of the aqueous sample, were investigated and optimized to obtain maximum method performance. Under the optimized instrumental analysis conditions, good linearity (r2 value ≥0.994) was achieved at the concentration range of 0.5-500 μg/L. Recoveries were in the range of 79.2-96.3 and 80.4-97.5% in selective-ion monitoring and multiple reaction monitoring (MRM) modes, respectively, at the spiking concentrations of 1, 5, and 10 μg/L. MRM mode showed better sensitivity, selectivity, and low-level detection (0.5 μg/L) of analytes. The novel MSPE method is a simple, cheap, rapid, and eco-friendly method for the determination of OPs in environmental water samples.

Characterization of Leucaena (Leucaena leucephala) oil by direct analysis in real time (DART) ion source and gas chromatography

International Nuclear Information System (INIS)

Alam, M.; Alandis, N.M.; Sharmin, E.; Ahmad, N.; Alrayes, B.F.; Ali, D.

2017-01-01

For the first time, we report the characterization of triacylglycerols and fatty acids in Leucaena (Leucaena leucephala) oil [LUCO], an unexplored nontraditional non-medicinal plant belonging to the family Fabaceae. LUCO was converted to fatty acid methyl esters (FAMEs). We analyzed the triacylglycerols (TAGs) of pure LUCO and their FAMEs by time-of-flight mass spectrometry (TOF-MS) followed by multivariate analysis for discrimination among the FAMEs. Our investigations for the analysis of LUCO samples represent noble features of glycerides. A new type of ion source, coupled with high-resolution TOF-MS was applied for the comprehensive analysis of triacylglycerols. The composition of fatty acid based LUCO oil was studied using Gas Chromatography (GC-FID). The major fatty acid components of LUCO oil are linoleic acid (52.08%) oleic acid (21.26%), palmitic acid (7.91%) and stearic acid (6.01%). A metal analysis in LUCO was done by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The structural elucidation and thermal stability of LUCO were studied by FT-IR, 1H NMR, 13C NMR spectroscopic techniques and TGA-DSC, respectively. We also measured the cytotoxicity of LUCO [es

Pressure-assisted introduction of urine samples into a short capillary for electrophoretic separation with contactless conductivity and UV spectrometry detection.

Science.gov (United States)

Makrlíková, Anna; Opekar, František; Tůma, Petr

2015-08-01

A computer-controlled hydrodynamic sample introduction method has been proposed for short-capillary electrophoresis. In the method, the BGE flushes sample from the loop of a six-way sampling valve and is carried to the injection end of the capillary. A short pressure impulse is generated in the electrolyte stream at the time when the sample zone is at the capillary, leading to injection of the sample into the capillary. Then the electrolyte flow is stopped and the separation voltage is turned on. This way of sample introduction does not involve movement of the capillary and both of its ends remain constantly in the solution during both sample injection and separation. The amount of sample introduced to the capillary is controlled by the duration of the pressure pulse. The new sample introduction method was tested in the determination of ammonia, creatinine, uric acid, and hippuric acid in human urine. The determination was performed in a capillary with an overall length of 10.5 cm, in two BGEs with compositions 50 mM MES + 5 mM NaOH (pH 5.1) and 1 M acetic acid + 1.5 mM crown ether 18-crown-6 (pH 2.4). A dual contactless conductivity/UV spectrometric detector was used for the detection. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiresidue analysis of persistent organic pollutants in contaminated soil using GC-LRMS, GC-HRMS and isotope dilution analysis

International Nuclear Information System (INIS)

Badea, Silviu-Laurentiu; Lundstedt, Staffan; Liljelind, Per; Tysklind, Mats

2009-01-01

In this study we evaluated a multiresidue analytical protocol for selected Persistent Organic Pollutants (POPs) in soil, that later can be used in adsorption and leaching studies. The method used was based on Soxhlet extraction and open column chromatographic fractionation and clean-up, as well as liquid-liquid extraction and acetylation for phenolic compounds. Target analytes, i.e. polychlorinated phenols (PCPhs), hexachlorobenzene (HCB), polychlorinated dibenzodioxins and furans (PCDDs/Fs), polychlorinated biphenyl (PCBs) PAHs, were detected and quantified using Gas Chromatography-Low Resolution Mass Spectrometry (GC-LRMS) and Gas Chromatography-High Resolution Mass Spectrometry (GC-HRMS) and isotope dilution methodology. Generally, the results show a good recovery and a low standard deviation for those isomers that have also a 13 C labeled compound present in the sample: 4-mono, 2,4 di, 2,4,5 tri, 2,3,4,5 and penta chlorinated phenols. Our results clearly demonstrate that it is possible to analyse a wide range of compounds in complex soil matrixes. (authors(

Is chondroitin sulfate responsible for the biological effects attributed to the GC protein-derived Macrophage Activating Factor (GcMAF)?

Science.gov (United States)

Ruggiero, Marco; Reinwald, Heinz; Pacini, Stefania

2016-09-01

We hypothesize that a plasma glycosaminoglycan, chondroitin sulfate, may be responsible for the biological and clinical effects attributed to the Gc protein-derived Macrophage Activating Factor (GcMAF), a protein that is extracted from human blood. Thus, Gc protein binds chondroitin sulfate on the cell surface and such an interaction may occur also in blood, colostrum and milk. This interpretation would solve the inconsistencies encountered in explaining the effects of GcMAF in vitro and in vivo. According to our model, the Gc protein or the GcMAF bind to chondroitin sulfate both on the cell surface and in bodily fluids, and the resulting multimolecular complexes, under the form of oligomers trigger a transmembrane signal or, alternatively, are internalized and convey the signal directly to the nucleus thus eliciting the diverse biological effects observed for both GcMAF and chondroitin sulfate. Copyright © 2016 Elsevier Ltd. All rights reserved.

Metabotyping of docosahexaenoic acid - treated Alzheimer's disease cell model.

Directory of Open Access Journals (Sweden)

Priti Bahety

Full Text Available BACKGROUND: Despite the significant amount of work being carried out to investigate the therapeutic potential of docosahexaenoic acid (DHA in Alzheimer's disease (AD, the mechanism by which DHA affects amyloid-β precursor protein (AβPP-induced metabolic changes has not been studied. OBJECTIVE: To elucidate the metabolic phenotypes (metabotypes associated with DHA therapy via metabonomic profiling of an AD cell model using gas chromatography time-of-flight mass spectrometry (GC/TOFMS. METHODS: The lysate and supernatant samples of CHO-wt and CHO-AβPP695 cells treated with DHA and vehicle control were collected and prepared for GC/TOFMS metabonomics profiling. The metabolic profiles were analyzed by multivariate data analysis techniques using SIMCA-P+ software. RESULTS: Both principal component analysis and subsequent partial least squares discriminant analysis revealed distinct metabolites associated with the DHA-treated and control groups. A list of statistically significant marker metabolites that characterized the metabotypes associated with DHA treatment was further identified. Increased levels of succinic acid, citric acid, malic acid and glycine and decreased levels of zymosterol, cholestadiene and arachidonic acid correlated with DHA treatment effect. DHA levels were also found to be increased upon treatment. CONCLUSION: Our study shows that DHA plays a role in mitigating AβPP-induced impairment in energy metabolism and inflammation by acting on tricarboxylic acid cycle, cholesterol biosynthesis pathway and fatty acid metabolism. The perturbations of these metabolic pathways by DHA in CHO-wt and CHO-AβPP695 cells shed further mechanistic insights on its neuroprotective actions.

Clandestine laboratory scene investigation and processing using portable GC/MS

Science.gov (United States)

Matejczyk, Raymond J.

1997-02-01

This presentation describes the use of portable gas chromatography/mass spectrometry for on-scene investigation and processing of clandestine laboratories. Clandestine laboratory investigations present special problems to forensic investigators. These crime scenes contain many chemical hazards that must be detected, identified and collected as evidence. Gas chromatography/mass spectrometry performed on-scene with a rugged, portable unit is capable of analyzing a variety of matrices for drugs and chemicals used in the manufacture of illicit drugs, such as methamphetamine. Technologies used to detect various materials at a scene have particular applications but do not address the wide range of samples, chemicals, matrices and mixtures that exist in clan labs. Typical analyses performed by GC/MS are for the purpose of positively establishing the identity of starting materials, chemicals and end-product collected from clandestine laboratories. Concerns for the public and investigator safety and the environment are also important factors for rapid on-scene data generation. Here is described the implementation of a portable multiple-inlet GC/MS system designed for rapid deployment to a scene to perform forensic investigations of clandestine drug manufacturing laboratories. GC/MS has long been held as the 'gold standard' in performing forensic chemical analyses. With the capability of GC/MS to separate and produce a 'chemical fingerprint' of compounds, it is utilized as an essential technique for detecting and positively identifying chemical evidence. Rapid and conclusive on-scene analysis of evidence will assist the forensic investigators in collecting only pertinent evidence thereby reducing the amount of evidence to be transported, reducing chain of custody concerns, reducing costs and hazards, maintaining sample integrity and speeding the completion of the investigative process.

SPME GC/MS Analysis of Three Ornithogalum L. species from Turkey

Directory of Open Access Journals (Sweden)

Gülin Renda

2016-01-01

Full Text Available In this study, a solid phase micro extraction (SPME method with gas chromatography-mass spectrometry (GC-MS was used for analysis of volatile compounds in flowers and bulbs of three Ornithogalum species. The samples of flowers and bulbs of Ornithogalum sigmoideum, Ornithogalum orthophyllum, Ornithogalum oligophyllum was separately analyzed by SPME-GC-MS. A comparison of volatile compounds was made between species and the parts studied. A total of 70 compounds were identified and different volatile compounds were determined in distinct parts of the species. The major volatile organic compound of the flowers of O. sigmoideum and O. ornithogalum was furan (54.5% and 57.0% respectively. For O. oligophyllum the major volatile organic compound was nonanal (19.2%. Analyses revealed that SPME-GC-MS method is appropriate for the analysis of volatile compounds of Ornithogalum species.

Depth-profile analysis of thermoelectric layers on Si wafers by pulsed r.f. glow discharge time-of-flight mass spectrometry

International Nuclear Information System (INIS)

Reinsberg, K.-G.; Schumacher, C.; Tempez, A.; Nielsch, K.; Broekaert, J.A.C.

2012-01-01

In this work the depth-profile analysis of thermoelectric layers deposited on Au and Cr covered Si wafers with the aid of pulsed radiofrequency glow discharge time-of-flight mass spectrometry (pulsed RF-GD-TOFMS also called plasma profiling TOFMS (PP-TOFMS™)) is described. For thermoelectric materials the depth resolutions obtained with both PP-TOFMS and secondary ion mass spectrometry (SIMS) are shown to be well comparable and in the order of the roughness of the corresponding layers (between 20 and 3700 nm). With both methods a direct solid analysis without any preparation steps is possible. In addition, the analysis of the samples with PP-TOFMS proved to be faster by a factor of 26 compared to SIMS, as sputtering rates were found to be 80 nm s −1 and 3 nm s −1 , respectively. For the analyzed samples the results of PP-TOFMS and SIMS show that a homogeneous deposition was obtained. Quantitative results for all samples could also be obtained directly by PP-TOFMS when the stoichiometry of one sample was determined beforehand for instance by inductively coupled plasma optical emission spectrometry (ICP-OES) and scanning electron microscopy energy dispersive X-ray fluorescence spectrometry (SEM-EDX). For Bi 2 Te 3 the standard deviation for the main component concentrations within one sample then is found to be between 1.1% and 1.9% and it is 3.6% from sample to sample. For Sb 2 Te 3 the values within one sample are from 1.7% to 4.2% and from sample to sample 5.3%, respectively. - Highlights: ► Depth resolution in sub micrometer size by glow discharge mass spectrometry. ► Bi and Sb telluride layers composition with GD-TOF-MS, ICP-OES and SEM-EDX agree. ► Homogeneities of layers measured with GD-TOF-MS and SIMS agree.

Identification of natural indigo in historical textiles by GC-MS.

Science.gov (United States)

Degani, Laura; Riedo, Chiara; Chiantore, Oscar

2015-02-01

The possibility of successfully applying a common GC-MS procedure for identification in one step of all types of dyes from plants of unknown origin and from historical objects is particularly attractive due to the high separation efficiency of the capillary columns, the MS detection sensitivity and the reproducibility of results. In this work, GC-MS analysis, previously and successfully used for the characterization of anthraquinones, flavonoids and tannins from plant extracts and historical samples, has been tested on indigoid dyestuffs. An analytical procedure based on the silylating agent N,O-bis-(trimethylsilyl)trifluoroacetamide (BSTFA) with 1% trimethylchlorosilane (TMCS) was applied to pure molecules of indigotin and indirubin and to plant extracts of Indigofera tinctoria L. and Isatis tinctoria L. Preliminary tests have been done to establish the chromatographic conditions and the derivatization amounts most suitable for the simultaneous detection of indigoid molecules and of the other natural compounds, such as fatty acids, carboxylic acids and sugars, contained within the plant extracts. In order to assess the capacity and the sensitivity of the analytical procedure in typical archaeometric applications, wool samples dyed in the laboratory with indigo were analysed by mimicking the sample amounts typically available with historical objects. The electron ionization (EI) spectra of the main silylated derivatives of indigoid molecules obtained in this way constitute the necessary data set for the characterization of natural extracts and historical works of art. Subsequently, the procedure has been applied to historical samples for the detection of indigo and of other dyestuffs eventually contained in samples. Additional information, useful for restoration and preservation of works of art, could be also obtained on the nature of stains and smudges present on the sampled textile material. The GC-MS method turns out to be an efficient and fast analytical tool

Method and apparatus for transport, introduction, atomization and excitation of emission spectrum for quantitative analysis of high temperature gas sample streams containing vapor and particulates without degradation of sample stream temperature

Science.gov (United States)

Eckels, David E.; Hass, William J.

1989-05-30

A sample transport, sample introduction, and flame excitation system for spectrometric analysis of high temperature gas streams which eliminates degradation of the sample stream by condensation losses.

Derivatizations for improved detection of alcohols by gas chromatography and photoionization detection (GC-PID)

International Nuclear Information System (INIS)

Krull, I.S.; Swartz, M.; Driscoll, J.N.

1984-01-01

Pentafluorophenyldimethylsilyl chloride (flophemesyl chloride, Fl) is a well known derivatization reagent for improved electron capture detection (ECD) in gas chromatography (GC)(GC-ECD), but it has never been utilized for improved detectability and sensitivity in GC-photoionization detection (GC-PID). A wide variety of flophemesyl alcohol derivatives have been used in order to show a new approach for realizing greatly reduced minimum detection limits (MDL) of virtually all alcohol derivatives in GC-PID analysis. This particular derivatization approach is inexpensive and easy to apply, leading to quantitative or near 100% conversion of the starting alcohols to the expected flophemesyl ethers (silyl ethers). Detection limits can be lowered by 2-3 orders of magnitude for such derivatives when compared with the starting alcohols, along with calibration plots that are linear over 5-7 orders of magnitude. Specific GC conditions have been developed for many flophemesyl derivatives, in all cases using packed columns. Both ECD and PID relative response factors (RRFs) and normalized RRFs have been determined, and such ratios can now be used for improved analytic identification from complex sample matrices, where appropriate. 28 references, 2 figures, 5 tables

Organotin analysis by gas chromatography-pulsed flame-photometric detection (GC-PFPD)

Energy Technology Data Exchange (ETDEWEB)

Leermakers, M.; Nuyttens, J.; Baeyens, W. [Vrije Universiteit Brussel, Analytical and Environmental Chemistry (ANCH), Brussel (Belgium)

2005-03-01

Monobutyltin (MBuT), dibutyltin (DBuT), and tributyltin (TBuT) mixtures have been separated and quantified by gas chromatography with pulsed flame-photometric detection (GC-PFPD). The compounds were first derivatized with NaBEt{sub 4}, then extracted with hexane and injected into the GC in splitless mode. Optimum GC and detector conditions were established. For GC, various injector temperatures and oven temperature programs were tested. For the PFPD detector, gate settings (gate delay and gate width) and detector temperature were optimized. A very good linearity was obtained up to 100-150 ppb for all organotin compounds. The detection limits obtained were: MBuT (0.7 ppb), DBuT (0.8 ppb), and TBuT (0.6 ppb). RSD for repeatability and reproducibility were well below 20% when the instrument was in routine operation. A biological sample (CRM 477) was also analyzed for organotins. Extraction from the biological matrix was performed with TMAH. Besides the increased risk of contamination, the derivatization step seemed to be critical. pH and amount of derivatizing agent were tested. When using an internal standard (TPrT) between 90% and 110% of the certified amounts of organotin were recovered. (orig.)

Evaluation of volatiles from two subtropical strawberry cultivars using GC-olfactometry, GC-MS odor activity values, and sensory analysis

Science.gov (United States)

Flavor profiles of two Florida strawberry cultivars were determined using GC-olfactometry,GC-MS, odor activity values (OAVs) and sensory analysis. Thirty-six aroma active compounds were detected using GC-O. Thirty-four were identified. The major odor-active compounds in decreasing intensity were: me...

At least two Fc Neu5Gc residues of monoclonal antibodies are required for binding to anti-Neu5Gc antibody.

Science.gov (United States)

Yu, Chuanfei; Gao, Kai; Zhu, Lei; Wang, Wenbo; Wang, Lan; Zhang, Feng; Liu, Chunyu; Li, Meng; Wormald, Mark R; Rudd, Pauline M; Wang, Junzhi

2016-01-29

Two non-human glycan epitopes, galactose-α-1,3-galactose (α-gal) and Neu5Gc-α-2-6-galactose (Neu5Gc) have been shown to be antigenic when attached to Fab oligosaccharides of monoclonal antibodies (mAbs) , while α-gal attached to Fc glycans was not. However, the antigenicity of Neu5Gc on the Fc glycans remains unclear in the context that most mAbs carry only Fc glycans. After studying two clinical mAbs carrying significant amounts of Fc Neu5Gc, we show that their binding activity with anti-Neu5Gc antibody resided in a small subset of mAbs carrying two or more Fc Neu5Gc, while mAbs harboring only one Neu5Gc showed no reactivity. Since most Neu5Gc epitopes were distributed singly on the Fc of mAbs, our results suggest that the potential antigenicity of Fc Neu5Gc is low. Our study could be referenced in the process design and optimization of mAb production in murine myeloma cells and in the quality control of mAbs for industries and regulatory authorities.

Double spike isotope dilution GC-ICP-MS for evaluation of mercury species transformation in real fish samples using ultrasound-assisted extraction.

Science.gov (United States)

Esteban-Fernández, Diego; Mirat, Manuela; de la Hinojosa, M Ignacia Martín; Alonso, J Ignacio García

2012-08-29

Sample preparation continues being a key factor to obtain fast and reliable quantification of Hg species. Assisted procedures enhance the efficiency and reduce the extraction time; however, collateral species transformations have been observed. Moreover, differential interconversions have been observed even between similar matrixes, which introduce an important uncertainty for real sample analysis. Trying to minimize Hg species transformations, we have tested a soft ultrasound-assisted extraction procedure. Species quantification and transformations have been evaluated using double spike isotope dilution analysis (IDA) together with gas chromatography inductively coupled plasma mass spectrometry (GC-ICP-MS) for a CRM material (Tort-2) and shark and swordfish muscle samples. Optimum extraction solution and sonication time led to quantitative extraction and accurate determination of MeHg and IHg in a short time, although different behaviors regarding species preservation were observed depending on the sample. Negligible species transformations were observed in the analysis of the CRM, while a small but significant demethylation factor was observed in the case of real samples. In comparison with other extraction procedures, species transformations became smaller, and fewer differences between fish species were found. Similar results were obtained for fresh and lyophilized samples of both fish samples, which permit one to analyze the fresh sample directly and save time in the sample preparation step. The high grade of species preservation and the affordability of the extraction procedure allow one to obtain accurate determinations even for routine laboratories using quantification techniques, which do not estimate species transformations.

On-line coupled LC-LC-GC for irradiation detection in complex lipid matrices

International Nuclear Information System (INIS)

Schulzki, G.; Spiegelberg, A.; Helle, N.; Boegl, K.W.; Schreiber, G.A.

1993-01-01

Since sample preparation with HPLC coupled on-line to the GC has been performed for only a few weeks in our laboratory, the results presented give a first look at what can be done by means of this technique. Even difficult samples as the described fish species, where an unequivocal identification regarding an irradiation treatment seemed to become a hopeless enterprise, could be managed. Because of the greater variety of fatty acids in fish ''new'' radiation-induced hydrocarbons were available. According to the theory of Nawar in addition to 16:2 and 17:2 hydrocarbons we have looked for in irradiated meat, further alkadienes appeared in irradiated fish, which were 14:2, 18:2 and 20:2. Analysis of the alkadiene-fraction, transferred to the GC after a two step LC clean up, resulted in an unequivocal identification of all fish samples as well as the fruits and sponge cake. For fruits and sponge cake the detection limit seems to be clearly below 0.5 kGy. It can further be lowered by increasing the amount of lipid whereas the upper limit for a certain LC column has to be determined. In contrast to these samples only qualitative results were obtained for fish. In the case of sponge cake for the first time irradiation of a component of a heat treated food was detected. Further investigations regarding reproducibility, dose dependence and detection limit have to be done. On-line coupled (LC-)LC-GC was proved to be a highly efficient method for analysis of complex samples. In contrast to off-line Florisil column chromatography only a small part of the initial lipid material is needed because the complete hydrocarbon fraction is transferred on-line to the GC. This offers the possibility to analyze even foods with a low fat content like various seafoods. Classification of the hydrocarbon fraction by a two step LC may facilitate the identification of the radiolytic products also if no mass spectrometric detection system is available. (orig./vhe)

Metal organic framework g-C3N4/MIL-53(Fe) heterojunctions with enhanced photocatalytic activity for Cr(VI) reduction under visible light

Science.gov (United States)

Huang, Wenyuan; Liu, Ning; Zhang, Xiaodong; Wu, Minghong; Tang, Liang

2017-12-01

In this study, hybrid nanocomposites based on Fe-based MOF and graphitic carbon nitride (g-C3N4) were developed by a facile solvothermal method. The as-prepared materials were characterized by XRD, FESEM, TEM, XPS and PL analysis. It was showed that the introduction of a certain amount of g-C3N4 on the surface of MIL-53(Fe) would improve the separation and migration rate of photo-induced charges, consequently resulting in the boost of photocatalytic efficiency. Compared with g-C3N4 and MIL-53(Fe), the CMFe composites displayed more excellent visible light-resposive photocatalytic activity for the reduction of Cr(VI). The optimal doping content of g-C3N4 in g-C3N4/MIL-53(Fe) composite was determined to be 3.0 wt%, and it showed about 2.1 and 2.0 times as high photocatalytic efficiency for the reduction of Cr(VI) as that of pure g-C3N4 and MIL-53(Fe), respectively. Meanwhile, the composite exhibited good reusability and stability in the process of cyclic experiments. A possible photocatalytic reaction mechanism was also investigated in detail by the related electrochemical analysis.

Active and realistic passive marijuana exposure tested by three immunoassays and GC/MS in urine

International Nuclear Information System (INIS)

Mule, S.J.; Lomax, P.; Gross, S.J.

1988-01-01

Human urine samples obtained before and after active and passive exposure to marijuana were analyzed by immune kits (Roche, Amersham, and Syva) and gas chromatography/mass spectrometry (GC/MS). Seven of eight subjects were positive for the entire five-day test period with one immune kit. The latter correlated with GC/MS in 98% of the samples. Passive inhalation experiments under conditions likely to reflect realistic exposure resulted consistently in less than 10 ng/mL of cannabinoids. The 10-100-ng/mL cannabinoid concentration range essential for detection of occasional and moderate marijuana users is thus unaffected by realistic passive inhalation

Active and realistic passive marijuana exposure tested by three immunoassays and GC/MS in urine

Energy Technology Data Exchange (ETDEWEB)

Mule, S.J.; Lomax, P.; Gross, S.J.

1988-05-01

Human urine samples obtained before and after active and passive exposure to marijuana were analyzed by immune kits (Roche, Amersham, and Syva) and gas chromatography/mass spectrometry (GC/MS). Seven of eight subjects were positive for the entire five-day test period with one immune kit. The latter correlated with GC/MS in 98% of the samples. Passive inhalation experiments under conditions likely to reflect realistic exposure resulted consistently in less than 10 ng/mL of cannabinoids. The 10-100-ng/mL cannabinoid concentration range essential for detection of occasional and moderate marijuana users is thus unaffected by realistic passive inhalation.

Accumulation of GC donor splice signals in mammals

Directory of Open Access Journals (Sweden)

Koonin Eugene V

2008-07-01

Full Text Available Abstract The GT dinucleotide in the first two intron positions is the most conserved element of the U2 donor splice signals. However, in a small fraction of donor sites, GT is replaced by GC. A substantial enrichment of GC in donor sites of alternatively spliced genes has been observed previously in human, nematode and Arabidopsis, suggesting that GC signals are important for regulation of alternative splicing. We used parsimony analysis to reconstruct evolution of donor splice sites and inferred 298 GT > GC conversion events compared to 40 GC > GT conversion events in primate and rodent genomes. Thus, there was substantive accumulation of GC donor splice sites during the evolution of mammals. Accumulation of GC sites might have been driven by selection for alternative splicing. Reviewers This article was reviewed by Jerzy Jurka and Anton Nekrutenko. For the full reviews, please go to the Reviewers' Reports section.

Analysis of odorous gases with simultaneous GC-MS and sensory determination

Energy Technology Data Exchange (ETDEWEB)

Orko, I.; Lehtomaeki, J.; Sandell, E.; Arnold, M. [VTT Chemical Technology, Espoo (Finland). Environmental Technology

1995-12-31

Industrial odorous off-gases can consist of hundreds of different compounds giving cause to odour annoyance in the vicinity of the odour-emitting plant. For the identification of the odorous components in the gas, traditional analytical methods are not always sufficient since the odour threshold values cannot often be found in literature. This report describes the development of a GC-MS sniffing port method for identifying odorous compounds in off-gases. In the method the sample is injected into a gas chromatograph and divided into two flows. The compounds in these sample flows are separated in two identical columns and detected simultaneously in a mass spectrometer and by sensory means. The olfactory detections are marked in the iongram and the odorous compounds are identified. Tenax TA adsorbent is generally used for collecting the odorous sample for analysis. The compounds are released from the adsorbent for analysis by thermal desorption. The report also describes a case study where the GC-MS sniffing port method was applied to a gaseous emission from a food factory. Over ten odorous compounds could be identified. (author)

Identification (GC and GC-MS) of unsaturated acetates in Elasmopalpus lignosellus and their biological activity (GC-EAD and EAG).

Science.gov (United States)

Jham, Gulab N; da Silva, Alexsandro A; Lima, Eraldo R; Viana, Paulo

2005-02-01

Two insect colonies of Elasmopalpus lignosellus were reared in our laboratory, the first being initiated from pupae obtained from a cornfield in the region of Sete Lagoas, Minas Gerais and the second from a cornfield in the region of Goiânia, Goiás. From the two colonies, two extracts were prepared from the pheromone glands of virgin E. lignosellus females. The extract obtained from the first colony was designated as extract 1 while the extract obtained from the second colony was designated as extract 2. Extract 1 was analyzed by gas chromatography-mass spectrometry (GC-MS) with (Z)-9-hexadecenyl acetate [(Z)-9-HDA] and (Z)-11-hexadecenyl acetate [(Z)-11-HDA] being identified and confirmed by the formation of DMDS derivatives. In addition, a third acetate, which could be either (E)-8-hexadecenyl acetate [(E)-8-HDA] or (E)-9-hexadecenyl acetate [(E)-9-HDA] was detected by GC-MS. Extract 2 was analyzed by gas chromatography (GC) and gas chromatography-electroannetography (GC-EAD) revealing the presence of (Z)-11-HDA and (Z)-9-TDA. In addition, the same compounds elicited a response with the E. lignosellus male antenna obtained from the second insect colony. Electroantennography (EAG) screening with the male E. lignosellus antenna (obtained from the second insect colony) was conducted with the 23 possible tetradecenyl acetates (TDA) and 22 hexadecenyl acetates (HDA) as standards. Out of the 23 TDA isomers evaluated, only (Z)-9-TDA elicited a response and out of the 22 HDA [(Z) and (E) isomers gamma2 to delta13] evaluated only (Z)-11-HDA elicited a response. The acetate compositions of two extracts obtained from insects originating from the two states (Minas Gerais and Goiás) of Brazil were different from one another as well as from that obtained from insects in Tifton, GA, USA. The bioactivity data (GC-EAD) of the extract 2 differed from those reported for the Tifton, GA, USA population. These data suggest polymorphism in relation to the insect populations found in

Congener Production in Blood Samples During Preparation and Storage

DEFF Research Database (Denmark)

Felby, Søren; Nielsen, Erik

1995-01-01

Retsmedicin, congener production, preparation, head space GC, acetone, isobutanol, storage, blood samples, n-propanol, methanol, methylethylketone......Retsmedicin, congener production, preparation, head space GC, acetone, isobutanol, storage, blood samples, n-propanol, methanol, methylethylketone...

The GC-heterogeneity of teleost fishes

Directory of Open Access Journals (Sweden)

Gautier Christian

2008-12-01

Full Text Available Abstract Background One of the most striking features of mammalian and birds chromosomes is the variation in the guanine-cytosine (GC content that occurs over scales of hundreds of kilobases to megabases; this is known as the "isochore" structure. Among other vertebrates the presence of isochores depends upon the taxon; isochore are clearly present in Crocodiles and turtles but fish genome seems very homogeneous on GC content. This has suggested a unique isochore origin after the divergence between Sarcopterygii and Actinopterygii, but before that between Sauropsida and mammals. However during more than 30 years of analysis, isochore characteristics have been studied and many important biological properties have been associated with the isochore structure of human genomes. For instance, the genes are more compact and their density is highest in GC rich isochores. Results This paper shows in teleost fish genomes the existence of "GC segmentation" sharing some of the characteristics of isochores although teleost fish genomes presenting a particular homogeneity in CG content. The entire genomes of T nigroviridis and D rerio are now available, and this has made it possible to check whether a mosaic structure associated with isochore properties can be found in these fishes. In this study, hidden Markov models were trained on fish genes (T nigroviridis and D rerio which were classified by using the isochore class of their human orthologous. A clear segmentation of these genomes was detected. Conclusion The GC content is an excellent indicator of isochores in heterogeneous genomes as mammals. The segmentation we obtained were well correlated with GC content and other properties associated to GC content such as gene density, the number of exons per gene and the length of introns. Therefore, the GC content is the main property that allows the detection of isochore but more biological properties have to be taken into account. This method allows detecting

Sensitivity of GC-EI/MS, GC-EI/MS/MS, LC-ESI/MS/MS, LC-Ag(+) CIS/MS/MS, and GC-ESI/MS/MS for analysis of anabolic steroids in doping control.

Science.gov (United States)

Cha, Eunju; Kim, Sohee; Kim, Ho Jun; Lee, Kang Mi; Kim, Ki Hun; Kwon, Oh-Seung; Lee, Jaeick

2015-01-01

This study compared the sensitivity of various separation and ionization methods, including gas chromatography with an electron ionization source (GC-EI), liquid chromatography with an electrospray ionization source (LC-ESI), and liquid chromatography with a silver ion coordination ion spray source (LC-Ag(+) CIS), coupled to a mass spectrometer (MS) for steroid analysis. Chromatographic conditions, mass spectrometric transitions, and ion source parameters were optimized. The majority of steroids in GC-EI/MS/MS and LC-Ag(+) CIS/MS/MS analysis showed higher sensitivities than those obtained with other analytical methods. The limits of detection (LODs) of 65 steroids by GC-EI/MS/MS, 68 steroids by LC-Ag(+) CIS/MS/MS, 56 steroids by GC-EI/MS, 54 steroids by LC-ESI/MS/MS, and 27 steroids by GC-ESI/MS/MS were below cut-off value of 2.0 ng/mL. LODs of steroids that formed protonated ions in LC-ESI/MS/MS analysis were all lower than the cut-off value. Several steroids such as unconjugated C3-hydroxyl with C17-hydroxyl structure showed higher sensitivities in GC-EI/MS/MS analysis relative to those obtained using the LC-based methods. The steroids containing 4, 9, 11-triene structures showed relatively poor sensitivities in GC-EI/MS and GC-ESI/MS/MS analysis. The results of this study provide information that may be useful for selecting suitable analytical methods for confirmatory analysis of steroids. Copyright © 2015 John Wiley & Sons, Ltd.

Atmospheric pressure gas chromatography–time-of-flight-mass spectrometry (APGC–ToF-MS) for the determination of regulated and emerging contaminants in aqueous samples after stir bar sorptive extraction (SBSE)

International Nuclear Information System (INIS)

Pintado-Herrera, Marina G.; González-Mazo, Eduardo; Lara-Martín, Pablo A.

2014-01-01

Graphical abstract: Examples of identification of target (triclosan, TCS) and non-target (tributhyl phosphate, TBP) compounds in environmental water samples by APGC–ToF-MS. Some confirmation criteria are shown (i.e. mass spectra, isotopic distribution, and accurate mass). - Highlights: • 102 regulated and emerging contaminants are simultaneously extracted by SBSE. • APGC–ToF-MS is presented as an alternative to EI for the analysis of microcontaminants. • Identification of non-target compounds in environmental matrices is also explored. - Abstract: This work presents the development, optimization and validation of a multi-residue method for the simultaneous determination of 102 contaminants, including fragrances, UV filters, repellents, endocrine disruptors, biocides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and several types of pesticides in aqueous matrices. Water samples were processed using stir bar sorptive extraction (SBSE) after the optimization of several parameters: agitation time, ionic strength, presence of organic modifiers, pH, and volume of the derivatizing agent. Target compounds were extracted from the bars by liquid desorption (LD). Separation, identification and quantification of analytes were carried out by gas chromatography (GC) coupled to time-of-flight (ToF-MS) mass spectrometry. A new ionization source, atmospheric pressure gas chromatography (APGC), was tested. The optimized protocol showed acceptable recovery percentages (50–100%) and limits of detection below 1 ng L −1 for most of the compounds. Occurrence of 21 out of 102 analytes was confirmed in several environmental aquatic matrices, including seawater, sewage effluent, river water and groundwater. Non-target compounds such as organophosphorus flame retardants were also identified in real samples by accurate mass measurement of their molecular ions using GC-APGC–ToF-MS. To the best of our knowledge, this is the first time that this

Atmospheric pressure gas chromatography–time-of-flight-mass spectrometry (APGC–ToF-MS) for the determination of regulated and emerging contaminants in aqueous samples after stir bar sorptive extraction (SBSE)

Energy Technology Data Exchange (ETDEWEB)

Pintado-Herrera, Marina G.; González-Mazo, Eduardo; Lara-Martín, Pablo A., E-mail: pablo.lara@uca.es

2014-12-03

Graphical abstract: Examples of identification of target (triclosan, TCS) and non-target (tributhyl phosphate, TBP) compounds in environmental water samples by APGC–ToF-MS. Some confirmation criteria are shown (i.e. mass spectra, isotopic distribution, and accurate mass). - Highlights: • 102 regulated and emerging contaminants are simultaneously extracted by SBSE. • APGC–ToF-MS is presented as an alternative to EI for the analysis of microcontaminants. • Identification of non-target compounds in environmental matrices is also explored. - Abstract: This work presents the development, optimization and validation of a multi-residue method for the simultaneous determination of 102 contaminants, including fragrances, UV filters, repellents, endocrine disruptors, biocides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and several types of pesticides in aqueous matrices. Water samples were processed using stir bar sorptive extraction (SBSE) after the optimization of several parameters: agitation time, ionic strength, presence of organic modifiers, pH, and volume of the derivatizing agent. Target compounds were extracted from the bars by liquid desorption (LD). Separation, identification and quantification of analytes were carried out by gas chromatography (GC) coupled to time-of-flight (ToF-MS) mass spectrometry. A new ionization source, atmospheric pressure gas chromatography (APGC), was tested. The optimized protocol showed acceptable recovery percentages (50–100%) and limits of detection below 1 ng L{sup −1} for most of the compounds. Occurrence of 21 out of 102 analytes was confirmed in several environmental aquatic matrices, including seawater, sewage effluent, river water and groundwater. Non-target compounds such as organophosphorus flame retardants were also identified in real samples by accurate mass measurement of their molecular ions using GC-APGC–ToF-MS. To the best of our knowledge, this is the first time that this

Chemical characterization of the acid alteration of diesel fuel: Non-targeted analysis by two-dimensional gas chromatography coupled with time-of-flight mass spectrometry with tile-based Fisher ratio and combinatorial threshold determination

Energy Technology Data Exchange (ETDEWEB)

Parsons, Brendon A.; Pinkerton, David K.; Wright, Bob W.; Synovec, Robert E.

2016-04-01

The illicit chemical alteration of petroleum fuels is of scientific interest, particularly to regulatory agencies which set fuel specifications, or excises based on those specifications. One type of alteration is the reaction of diesel fuel with concentrated sulfuric acid. Such reactions are known to subtly alter the chemical composition of the fuel, particularly the aromatic species native to the fuel. Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC × GC–TOFMS) is ideally suited for the analysis of diesel fuel, but may provide the analyst with an overwhelming amount of data, particularly in sample-class comparison experiments comprised of many samples. The tile-based Fisher-ratio (F-ratio) method reduces the abundance of data in a GC × GC–TOFMS experiment to only the peaks which significantly distinguish the unaltered and acid altered sample classes. Three samples of diesel fuel from different filling stations were each altered to discover chemical features, i.e., analyte peaks, which were consistently changed by the acid reaction. Using different fuels prioritizes the discovery of features which are likely to be robust to the variation present between fuel samples and which will consequently be useful in determining whether an unknown sample has been acid altered. The subsequent analysis confirmed that aromatic species are removed by the acid alteration, with the degree of removal consistent with predicted reactivity toward electrophilic aromatic sulfonation. Additionally, we observed that alkenes and alkynes were also removed from the fuel, and that sulfur dioxide or compounds that degrade to sulfur dioxide are generated by the acid alteration. In addition to applying the previously reported tile-based F-ratio method, this report also expands null distribution analysis to algorithmically determine an F-ratio threshold to confidently select only the features which are sufficiently class-distinguishing. When

Analysis of intra-genomic GC content homogeneity within prokaryotes

DEFF Research Database (Denmark)

Bohlin, J; Snipen, L; Hardy, S.P.

2010-01-01

the GC content varies within microbial genomes to assess whether this property can be associated with certain biological functions related to the organism's environment and phylogeny. We utilize a new quantity GCVAR, the intra-genomic GC content variability with respect to the average GC content......Bacterial genomes possess varying GC content (total guanines (Gs) and cytosines (Cs) per total of the four bases within the genome) but within a given genome, GC content can vary locally along the chromosome, with some regions significantly more or less GC rich than on average. We have examined how...... both aerobic and facultative microbes. Although an association has previously been found between mean genomic GC content and oxygen requirement, our analysis suggests that no such association exits when phylogenetic bias is accounted for. A significant association between GCVAR and mean GC content...

The Met Office Global Coupled Model 3.0 and 3.1 (GC3.0 and GC3.1) Configurations

Science.gov (United States)

Williams, K. D.; Copsey, D.; Blockley, E. W.; Bodas-Salcedo, A.; Calvert, D.; Comer, R.; Davis, P.; Graham, T.; Hewitt, H. T.; Hill, R.; Hyder, P.; Ineson, S.; Johns, T. C.; Keen, A. B.; Lee, R. W.; Megann, A.; Milton, S. F.; Rae, J. G. L.; Roberts, M. J.; Scaife, A. A.; Schiemann, R.; Storkey, D.; Thorpe, L.; Watterson, I. G.; Walters, D. N.; West, A.; Wood, R. A.; Woollings, T.; Xavier, P. K.

2018-02-01

The Global Coupled 3 (GC3) configuration of the Met Office Unified Model is presented. Among other applications, GC3 is the basis of the United Kingdom's submission to the Coupled Model Intercomparison Project 6 (CMIP6). This paper documents the model components that make up the configuration (although the scientific descriptions of these components are in companion papers) and details the coupling between them. The performance of GC3 is assessed in terms of mean biases and variability in long climate simulations using present-day forcing. The suitability of the configuration for predictability on shorter time scales (weather and seasonal forecasting) is also briefly discussed. The performance of GC3 is compared against GC2, the previous Met Office coupled model configuration, and against an older configuration (HadGEM2-AO) which was the submission to CMIP5. In many respects, the performance of GC3 is comparable with GC2, however, there is a notable improvement in the Southern Ocean warm sea surface temperature bias which has been reduced by 75%, and there are improvements in cloud amount and some aspects of tropical variability. Relative to HadGEM2-AO, many aspects of the present-day climate are improved in GC3 including tropospheric and stratospheric temperature structure, most aspects of tropical and extratropical variability and top-of-atmosphere and surface fluxes. A number of outstanding errors are identified including a residual asymmetric sea surface temperature bias (cool northern hemisphere, warm Southern Ocean), an overly strong global hydrological cycle and insufficient European blocking.

Synthesis of g-C3N4/Fe3O4 nanocomposites and application as a new sorbent for solid phase extraction of polycyclic aromatic hydrocarbons in water samples.

Science.gov (United States)

Wang, Man; Cui, Shihai; Yang, Xiaodi; Bi, Wentao

2015-01-01

An easy preparation of g-C3N4/Fe3O4 nanocomposites by chemical co-precipitation has been demonstrated. The as-prepared materials were characterized by X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis. The high affinity of g-C3N4 toward polycyclic aromatic hydrocarbons and the magnetic behavior of Fe3O4 were combined to provide an efficient and simple magnetic solid phase extraction (MSPE). The adsorption and desorption of polycyclic aromatic hydrocarbons on g-C3N4/Fe3O4 were examined. Different factors affecting the magnetic solid phase extraction of polycyclic aromatic hydrocarbons were assessed in terms of adsorption, desorption, and recovery. Under the optimized conditions, the proposed method showed good limits of detection (LOD, S/N=3) in the range of 0.05-0.1 ng mL(-1) and precision in the range of 1.8-5.3% (RSDs, n=3). This method was also successfully applied to the analysis of real water samples; good spiked recoveries over the range of 80.0-99.8% were obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

Modern survey sampling

CERN Document Server

Chaudhuri, Arijit

2014-01-01

Exposure to SamplingAbstract Introduction Concepts of Population, Sample, and SamplingInitial RamificationsAbstract Introduction Sampling Design, Sampling SchemeRandom Numbers and Their Uses in Simple RandomSampling (SRS)Drawing Simple Random Samples with and withoutReplacementEstimation of Mean, Total, Ratio of Totals/Means:Variance and Variance EstimationDetermination of Sample SizesA.2 Appendix to Chapter 2 A.More on Equal Probability Sampling A.Horvitz-Thompson EstimatorA.SufficiencyA.LikelihoodA.Non-Existence Theorem More Intricacies Abstract Introduction Unequal Probability Sampling StrategiesPPS Sampling Exploring Improved WaysAbstract Introduction Stratified Sampling Cluster SamplingMulti-Stage SamplingMulti-Phase Sampling: Ratio and RegressionEstimationviiviii ContentsControlled SamplingModeling Introduction Super-Population ModelingPrediction Approach Model-Assisted Approach Bayesian Methods Spatial SmoothingSampling on Successive Occasions: Panel Rotation Non-Response and Not-at-Homes Weighting Adj...

Characterization of Leucaena (Leucaena leucephala) oil by direct analysis in real time (DART) ion source and gas chromatography; Caracterización del aceite de Leucaena (Leucaena leucocephala) por análisis directo en tiempo real (DART) y cromatografía de gases

Energy Technology Data Exchange (ETDEWEB)

Alam, M.; Alandis, N.M.; Sharmin, E.; Ahmad, N.; Alrayes, B.F.; Ali, D.

2017-07-01

For the first time, we report the characterization of triacylglycerols and fatty acids in Leucaena (Leucaena leucephala) oil [LUCO], an unexplored nontraditional non-medicinal plant belonging to the family Fabaceae. LUCO was converted to fatty acid methyl esters (FAMEs). We analyzed the triacylglycerols (TAGs) of pure LUCO and their FAMEs by time-of-flight mass spectrometry (TOF-MS) followed by multivariate analysis for discrimination among the FAMEs. Our investigations for the analysis of LUCO samples represent noble features of glycerides. A new type of ion source, coupled with high-resolution TOF-MS was applied for the comprehensive analysis of triacylglycerols. The composition of fatty acid based LUCO oil was studied using Gas Chromatography (GC-FID). The major fatty acid components of LUCO oil are linoleic acid (52.08%) oleic acid (21.26%), palmitic acid (7.91%) and stearic acid (6.01%). A metal analysis in LUCO was done by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The structural elucidation and thermal stability of LUCO were studied by FT-IR, 1H NMR, 13C NMR spectroscopic techniques and TGA-DSC, respectively. We also measured the cytotoxicity of LUCO [Spanish] Se presenta por primera vez la caracterización de triacilgliceroles y ácidos grasos del aceite de Leucaena (Leucaena leucephala) [LUCO], una planta no medicinal, no tradicional y no explorada, perteneciente a la familia Fabaceae. Se analizaron triacilgliceroles (TAGs) de LUCO y sus FAMEs por espectrometría de masas de tiempo de vuelo (TOF-MS) seguido de análisis multivariante para discriminación entre los FAME. Nuestras investigaciones para el análisis de muestras de LUCO presentaron características propias de los glicéridos. Un nuevo tipo de fuente de iones, junto con alta resolución TOF-MS se aplicó para el análisis exhaustivo de triacilgliceroles. La composición de aceite de LUCO basado en ácidos grasos se estudió usando Cromatografía de Gas (GC-FID). Los principales

TargetSearch--a Bioconductor package for the efficient preprocessing of GC-MS metabolite profiling data.

Science.gov (United States)

Cuadros-Inostroza, Alvaro; Caldana, Camila; Redestig, Henning; Kusano, Miyako; Lisec, Jan; Peña-Cortés, Hugo; Willmitzer, Lothar; Hannah, Matthew A

2009-12-16

Metabolite profiling, the simultaneous quantification of multiple metabolites in an experiment, is becoming increasingly popular, particularly with the rise of systems-level biology. The workhorse in this field is gas-chromatography hyphenated with mass spectrometry (GC-MS). The high-throughput of this technology coupled with a demand for large experiments has led to data pre-processing, i.e. the quantification of metabolites across samples, becoming a major bottleneck. Existing software has several limitations, including restricted maximum sample size, systematic errors and low flexibility. However, the biggest limitation is that the resulting data usually require extensive hand-curation, which is subjective and can typically take several days to weeks. We introduce the TargetSearch package, an open source tool which is a flexible and accurate method for pre-processing even very large numbers of GC-MS samples within hours. We developed a novel strategy to iteratively correct and update retention time indices for searching and identifying metabolites. The package is written in the R programming language with computationally intensive functions written in C for speed and performance. The package includes a graphical user interface to allow easy use by those unfamiliar with R. TargetSearch allows fast and accurate data pre-processing for GC-MS experiments and overcomes the sample number limitations and manual curation requirements of existing software. We validate our method by carrying out an analysis against both a set of known chemical standard mixtures and of a biological experiment. In addition we demonstrate its capabilities and speed by comparing it with other GC-MS pre-processing tools. We believe this package will greatly ease current bottlenecks and facilitate the analysis of metabolic profiling data.

In situ studies of pesticides photodegradation on soils using PD-TOFMS technique

Science.gov (United States)

Thomas, J. P.; Bejjani, A.; Nsouli, B.; Gardon, A.; Chovelon, J. M.

2009-01-01

As we have demonstrated that plasma desorption time-of-flight mass spectrometry (PD-TOFMS) is well adapted to the direct characterization of pesticides adsorbed on agricultural soils the technique has been applied for the first time to the study of their evolution under sunlight-like irradiation. Two pesticides have been selected: norflurazon which is the most documentated (both from the literature and from our previous experiments) and oxyfluorfen in order to assess the capability of the technique. The photodegradation process has been investigated both for a deposit onto a metallic substrate and for a soil impregnated with the product. For norflurazon degradation parameters have been extracted from the yield variation of ions representative of the molecule and breakdown products and particularly the time required for 50% dissipation of their initial concentration (DT50 values). The comparison between deposits and soils indicates clearly that the degradation is slower in the latter case with an increase of about 3.5 for the DT50 of the molecule, and about 2 for its breakdown products. These values are in agreement with the decays of other ions. As expected, the degradation is faster when the UV of the sunlight is unfiltered, more significantly for the breakdown products. This is also observed for the oxyfluorfen deposited onto aluminium although at a lower level (twice less). The trends are only qualitative for the impregnated soil but definitely there. A discussion is presented for the interpretation of the photodegradation process in both cases together with suggestions of improvement in the data acquisition.

Fluorescence imaging of ion distributions in an inductively coupled plasma with laser ablation sample introduction

International Nuclear Information System (INIS)

Moses, Lance M.; Ellis, Wade C.; Jones, Derick D.; Farnsworth, Paul B.

2015-01-01

High-resolution images of the spatial distributions of Sc II, Ca II, and Ba II ion densities in the 10 mm upstream from the sampling cone in a laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS) were obtained using planar laser induced fluorescence. Images were obtained for each analyte as a function of the carrier gas flow rate with laser ablation (LA) sample introduction and compared to images with solution nebulization (SN) over the same range of flow rates. Additionally, images were obtained using LA at varying fluences and with varying amounts of helium added to a constant flow of argon gas. Ion profiles in SN images followed a pattern consistent with previous work: increasing gas flow caused a downstream shift in the ion profiles. When compared to SN, LA led to ion profiles that were much narrower radially and reached a maximum near the sampling cone at higher flow rates. Increasing the fluence led to ions formed in the ICP over greater axial and radial distances. The addition of He to the carrier gas prior to the ablation cell led to an upstream shift in the position of ionization and lower overall fluorescence intensities. - Highlights: • We map distributions of analytes in the ICP using laser ablation sample introduction. • We compare images from laser ablation with those from a pneumatic nebulizer. • We document the effects of water added to the laser ablation aerosol. • We compare distributions from a metal to those from crystalline solids. • We document the effect of laser fluence on ion distributions

New high temperature plasmas and sample introduction systems for analytical atomic emission and mass spectrometry

International Nuclear Information System (INIS)

Montaser, A.

1993-01-01

In this research, new high-temperature plasmas and new sample introduction systems are explored for rapid elemental and isotopic analysis of gases, solutions, and solids using mass spectrometry and atomic emission spectrometry. During the period January 1993--December 1993, emphasis was placed on (a) analytical investigations of atmospheric-pressure helium inductively coupled plasma (He ICP) that are suitable for atomization, excitation, and ionization of elements possessing high excitation and ionization energies; (b) simulation and computer modeling of plasma sources to predict their structure and fundamental and analytical properties without incurring the enormous cost of experimental studies; (c) spectrosopic imaging and diagnostic studies of high-temperature plasmas; (d) fundamental studies of He ICP discharges and argon-nitrogen plasma by high-resolution Fourier transform spectrometry; and (e) fundamental and analytical investigation of new, low-cost devices as sample introduction systems for atomic spectrometry and examination of new diagnostic techniques for probing aerosols. Only the most important achievements are included in this report to illustrate progress and obstacles. Detailed descriptions of the authors' investigations are outlined in the reprints and preprints that accompany this report. The technical progress expected next year is briefly described at the end of this report

Quantification of acetaminophen (paracetamol) in human plasma and urine by stable isotope-dilution GC-MS and GC-MS/MS as pentafluorobenzyl ether derivative.

Science.gov (United States)

Trettin, Arne; Zoerner, Alexander A; Böhmer, Anke; Gutzki, Frank-Mathias; Stichtenoth, Dirk O; Jordan, Jens; Tsikas, Dimitrios

2011-08-01

We report on the quantitative determination of acetaminophen (paracetamol; NAPAP-d(0)) in human plasma and urine by GC-MS and GC-MS/MS in the electron-capture negative-ion chemical ionization (ECNICI) mode after derivatization with pentafluorobenzyl (PFB) bromide (PFB-Br). Commercially available tetradeuterated acetaminophen (NAPAP-d(4)) was used as the internal standard. NAPAP-d(0) and NAPAP-d(4) were extracted from 100-μL aliquots of plasma and urine with 300 μL ethyl acetate (EA) by vortexing (60s). After centrifugation the EA phase was collected, the solvent was removed under a stream of nitrogen gas, and the residue was reconstituted in acetonitrile (MeCN, 100 μL). PFB-Br (10 μL, 30 vol% in MeCN) and N,N-diisopropylethylamine (10 μL) were added and the mixture was incubated for 60 min at 30 °C. Then, solvents and reagents were removed under nitrogen and the residue was taken up with 1000 μL of toluene, from which 1-μL aliquots were injected in the splitless mode. GC-MS quantification was performed by selected-ion monitoring ions due to [M-PFB](-) and [M-PFB-H](-), m/z 150 and m/z 149 for NAPAP-d(0) and m/z 154 and m/z 153 for NAPAP-d(4), respectively. GC-MS/MS quantification was performed by selected-reaction monitoring the transition m/z 150 → m/z 107 and m/z 149 → m/z 134 for NAPAP-d(0) and m/z 154 → m/z 111 and m/z 153 → m/z 138 for NAPAP-d(4). The method was validated for human plasma (range, 0-130 μM NAPAP-d(0)) and urine (range, 0-1300 μM NAPAP-d(0)). Accuracy (recovery, %) ranged between 89 and 119%, and imprecision (RSD, %) was below 19% in these matrices and ranges. A close correlation (r>0.999) was found between the concentrations measured by GC-MS and GC-MS/MS. By this method, acetaminophen can be reliably quantified in small plasma and urine sample volumes (e.g., 10 μL). The analytical performance of the method makes it especially useful in pediatrics. Copyright © 2011 Elsevier B.V. All rights reserved.

Volume overload cleanup: An approach for on-line SPE-GC, GPC-GC, and GPC-SPE-GC

NARCIS (Netherlands)

Kerkdijk, H.; Mol, H.G.J.; Nagel, B. van der

2007-01-01

A new concept for cleanup, based on volume overloading of the cleanup column, has been developed for on-line coupling of gel permeation chromatography (GPC), solid-phase extraction (SPE), or both, to gas chromatography (GC). The principle is outlined and the applicability demonstrated by the

Rapid analysis for 567 pesticides and endocrine disrupters by GC/MS using deconvolution reporting software

Energy Technology Data Exchange (ETDEWEB)

Wylie, P.; Szelewski, M.; Meng, Chin-Kai [Agilent Technologies, Wilmington, DE (United States)

2004-09-15

More than 700 pesticides are approved for use around the world, many of which are suspected endocrine disrupters. Other pesticides, though no longer used, persist in the environment where they bioaccumulate in the flora and fauna. Analytical methods target only a subset of the possible compounds. The analysis of food and environmental samples for pesticides is usually complicated by the presence of co-extracted natural products. Food or tissue extracts can be exceedingly complex matrices that require several stages of sample cleanup prior to analysis. Even then, it can be difficult to detect trace levels of contaminants in the presence of the remaining matrix. For efficiency, multi-residue methods (MRMs) must be used to analyze for most pesticides. Traditionally, these methods have relied upon gas chromatography (GC) with a constellation of element-selective detectors to locate pesticides in the midst of a variable matrix. GC with mass spectral detection (GC/MS) has been widely used for confirmation of hits. Liquid chromatography (LC) has been used for those compounds that are not amenable to GC. Today, more and more pesticide laboratories are relying upon LC with mass spectral detection (LC/MS) and GC/MS as their primary analytical tools. Still, most MRMs are target compound methods that look for a small subset of the possible pesticides. Any compound not on the target list is likely to be missed by these methods. Using the techniques of retention time locking (RTL) and RTL database searching together with spectral deconvolution, a method has been developed to screen for 567 pesticides and suspected endocrine disrupters in a single GC/MS analysis. Spectral deconvolution helps to identify pesticides even when they co-elute with matrix compounds while RTL helps to eliminate false positives and gives greater confidence in the results.

Radiofrequency glow discharge time of flight mass spectrometry: pulsed vs. continuous mode

International Nuclear Information System (INIS)

Lobo, L.; Pereiro, R.; Sanz-Medel, A.; Bordel, N.; Tempez, A.; Chapon, P.; Hohl, M.; Michler, J.

2009-01-01

Full text: Glow discharge (GD) is a well established tool for the direct analysis of solids. The application field of the original direct current GD, restricted to conductive samples, has been extended by radiofrequency powered GDs that can be applied for conductive and non-conductive samples. Moreover, the introduction of pulsed GD has opened the possibility of applying higher instantaneous powers that can improve the atomization-ionization processes and therefore the sensitivity. Furthermore, pulsed-GD may enable temporal separation of discharge gas species from the sample ions. In this work the analytical performances of radiofrequency and pulsed radiofrequency glow discharges are evaluated by using a time of flight mass analyzer (TOFMS). (author)

Synthesis of g-C3N4/Ag3PO4 heterojunction with enhanced photocatalytic performance

International Nuclear Information System (INIS)

He, Peizhi; Song, Limin; Zhang, Shujuan; Wu, Xiaoqing; Wei, Qingwu

2014-01-01

Graphical abstract: g-C 3 N 4 /Ag 3 PO 4 heterojunction photocatalyst with visible-light response was prepared by a facile coprecipitation method. The results show that g-C 3 N 4 /Ag 3 PO 4 possesses a much higher activity for the decomposition of RhB than that of the pure Ag 3 PO 4 particles. The most mechanism is that g-C 3 N 4 /Ag 3 PO 4 heterojunction photocatalyst can efficiently separate the photogenerated electron–hole pairs, enhancing the photocatalytic activity of g-C 3 N 4 /Ag 3 PO 4 composites. - Highlights: • g-C 3 N 4 /Ag 3 PO 4 heterojunction showed much higher activity than that of Ag 3 PO 4 . • The high activity could be attributed to g-C 3 N 4 for modifying Ag 3 PO 4 . • More ·OH radicals may be significant reason to improve Ag 3 PO 4 activity. - Abstract: g-C 3 N 4 /Ag 3 PO 4 heterojunction photocatalyst with visible-light response was prepared by a facile coprecipitation method. The photocatalysts were characterized by X-ray powder diffraction, transmission electron microscopy, UV–vis absorption spectroscopy and Fourier transform infrared spectroscopy. The photocatalytic activities of the obtained samples were tested by using Rhodamine B (RhB) as the degradation target under visible light irradiation. g-C 3 N 4 /Ag 3 PO 4 decomposed RhB more effectively than the pure Ag 3 PO 4 particles did, and 2 wt.% g-C 3 N 4 had the highest activity. Furthermore, 2 wt.% g-C 3 N 4 /Ag 3 PO 4 degraded high-concentration RhB more potently than unmodified Ag 3 PO 4 did, probably because g-C 3 N 4 /Ag 3 PO 4 heterojunction photocatalyst enhanced the photocatalytic activity by efficiently separating the photogenerated electron–hole pairs

Sample preparation techniques for the determination of natural 15N/14N variations in amino acids by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS).

Science.gov (United States)

Hofmann, D; Gehre, M; Jung, K

2003-09-01

In order to identify natural nitrogen isotope variations of biologically important amino acids four derivatization reactions (t-butylmethylsilylation, esterification with subsequent trifluoroacetylation, acetylation and pivaloylation) were tested with standard mixtures of 17 proteinogenic amino acids and plant (moss) samples using GC-C-IRMS. The possible fractionation of the nitrogen isotopes, caused for instance by the formation of multiple reaction products, was investigated. For biological samples, the esterification of the amino acids with subsequent trifluoroacetylation is recommended for nitrogen isotope ratio analysis. A sample preparation technique is described for the isotope ratio mass spectrometric analysis of amino acids from the non-protein (NPN) fraction of terrestrial moss. 14N/15N ratios from moss (Scleropodium spec.) samples from different anthropogenically polluted areas were studied with respect to ecotoxicologal bioindication.

APTIMA assay on SurePath liquid-based cervical samples compared to endocervical swab samples facilitated by a real time database

Directory of Open Access Journals (Sweden)

Khader Samer

2010-01-01

Full Text Available Background: Liquid-based cytology (LBC cervical samples are increasingly being used to test for pathogens, including: HPV, Chlamydia trachomatis (CT and Neisseria gonorrhoeae (GC using nucleic acid amplification tests. Several reports have shown the accuracy of such testing on ThinPrep (TP LBC samples. Fewer studies have evaluated SurePath (SP LBC samples, which utilize a different specimen preservative. This study was undertaken to assess the performance of the Aptima Combo 2 Assay (AC2 for CT and GC on SP versus endocervical swab samples in our laboratory. Materials and Methods: The live pathology database of Montefiore Medical Center was searched for patients with AC2 endocervical swab specimens and SP Paps taken the same day. SP samples from CT- and/or GC-positive endocervical swab patients and randomly selected negative patients were studied. In each case, 1.5 ml of the residual SP vial sample, which was in SP preservative and stored at room temperature, was transferred within seven days of collection to APTIMA specimen transfer tubes without any sample or patient identifiers. Blind testing with the AC2 assay was performed on the Tigris DTS System (Gen-probe, San Diego, CA. Finalized SP results were compared with the previously reported endocervical swab results for the entire group and separately for patients 25 years and younger and patients over 25 years. Results: SP specimens from 300 patients were tested. This included 181 swab CT-positive, 12 swab GC-positive, 7 CT and GC positive and 100 randomly selected swab CT and GC negative patients. Using the endocervical swab results as the patient′s infection status, AC2 assay of the SP samples showed: CT sensitivity 89.3%, CT specificity 100.0%; GC sensitivity and specificity 100.0%. CT sensitivity for patients 25 years or younger was 93.1%, versus 80.7% for patients over 25 years, a statistically significant difference (P = 0.02. Conclusions: Our results show that AC2 assay of 1.5 ml SP

Analysis of nitrosamines in water by automated SPE and isotope dilution GC/HRMS Occurrence in the different steps of a drinking water treatment plant, and in chlorinated samples from a reservoir and a sewage treatment plant effluent.

Science.gov (United States)

Planas, Carles; Palacios, Oscar; Ventura, Francesc; Rivera, Josep; Caixach, Josep

2008-08-15

A method based on automated solid-phase extraction (SPE) and isotope dilution gas chromatography/high resolution mass spectrometry (GC/HRMS) has been developed for the analysis of nine nitrosamines in water samples. The combination of automated SPE and GC/HRMS for the analysis of nitrosamines has not been reported previously. The method shows as advantages the selectivity and sensitivity of GC/HRMS analysis and the high efficiency of automated SPE with coconut charcoal EPA 521 cartridges. Low method detection limits (MDLs) were achieved, along with a greater facility of the procedure and less dependence on the operator with regard to the methods based on manual SPE. Quality requirements for isotope dilution-based methods were accomplished for most analysed nitrosamines, regarding to trueness (80-120%), method precision (water samples (16 samples from a drinking water treatment plant {DWTP}, 2 chlorinated samples from a sewage treatment plant {STP} effluent, and 1 chlorinated sample from a reservoir) were analysed. Concentrations of nitrosamines in the STP effluent were 309.4 and 730.2 ng/L, being higher when higher doses of chlorine were applied. N-Nitrosodimethylamine (NDMA) and N-nitrosodiethylamine (NDEA) were the main compounds identified in the STP effluent, and NDEA was detected above 200 ng/L, regulatory level for NDMA in effluents stated in Ontario (Canada). Lower concentrations of nitrosamines were found in the reservoir (20.3 ng/L) and in the DWTP samples (n.d. -28.6 ng/L). NDMA and NDEA were respectively found in the reservoir and in treated and highly chlorinated DWTP samples at concentrations above 10 ng/L (guide value established in different countries). The highest concentrations of nitrosamines were found after chlorination and ozonation processes (ozonated, treated and highly chlorinated water) in DWTP samples.

TargetSearch - a Bioconductor package for the efficient preprocessing of GC-MS metabolite profiling data

Science.gov (United States)

2009-01-01

Background Metabolite profiling, the simultaneous quantification of multiple metabolites in an experiment, is becoming increasingly popular, particularly with the rise of systems-level biology. The workhorse in this field is gas-chromatography hyphenated with mass spectrometry (GC-MS). The high-throughput of this technology coupled with a demand for large experiments has led to data pre-processing, i.e. the quantification of metabolites across samples, becoming a major bottleneck. Existing software has several limitations, including restricted maximum sample size, systematic errors and low flexibility. However, the biggest limitation is that the resulting data usually require extensive hand-curation, which is subjective and can typically take several days to weeks. Results We introduce the TargetSearch package, an open source tool which is a flexible and accurate method for pre-processing even very large numbers of GC-MS samples within hours. We developed a novel strategy to iteratively correct and update retention time indices for searching and identifying metabolites. The package is written in the R programming language with computationally intensive functions written in C for speed and performance. The package includes a graphical user interface to allow easy use by those unfamiliar with R. Conclusions TargetSearch allows fast and accurate data pre-processing for GC-MS experiments and overcomes the sample number limitations and manual curation requirements of existing software. We validate our method by carrying out an analysis against both a set of known chemical standard mixtures and of a biological experiment. In addition we demonstrate its capabilities and speed by comparing it with other GC-MS pre-processing tools. We believe this package will greatly ease current bottlenecks and facilitate the analysis of metabolic profiling data. PMID:20015393

TargetSearch - a Bioconductor package for the efficient preprocessing of GC-MS metabolite profiling data

Directory of Open Access Journals (Sweden)

Lisec Jan

2009-12-01

Full Text Available Abstract Background Metabolite profiling, the simultaneous quantification of multiple metabolites in an experiment, is becoming increasingly popular, particularly with the rise of systems-level biology. The workhorse in this field is gas-chromatography hyphenated with mass spectrometry (GC-MS. The high-throughput of this technology coupled with a demand for large experiments has led to data pre-processing, i.e. the quantification of metabolites across samples, becoming a major bottleneck. Existing software has several limitations, including restricted maximum sample size, systematic errors and low flexibility. However, the biggest limitation is that the resulting data usually require extensive hand-curation, which is subjective and can typically take several days to weeks. Results We introduce the TargetSearch package, an open source tool which is a flexible and accurate method for pre-processing even very large numbers of GC-MS samples within hours. We developed a novel strategy to iteratively correct and update retention time indices for searching and identifying metabolites. The package is written in the R programming language with computationally intensive functions written in C for speed and performance. The package includes a graphical user interface to allow easy use by those unfamiliar with R. Conclusions TargetSearch allows fast and accurate data pre-processing for GC-MS experiments and overcomes the sample number limitations and manual curation requirements of existing software. We validate our method by carrying out an analysis against both a set of known chemical standard mixtures and of a biological experiment. In addition we demonstrate its capabilities and speed by comparing it with other GC-MS pre-processing tools. We believe this package will greatly ease current bottlenecks and facilitate the analysis of metabolic profiling data.

Micro-pyrolysis of technical lignins in a new modular rig and product analysis by GC-MS/FID and GC x GC-TOFMS/FID

NARCIS (Netherlands)

Windt, Michael; Meier, Dietrich; Marsman, Jan Henk; Heeres, Hero Jan; de Koning, Sjaak

A new offline-pyrolysis rig has been designed to allow multifunctional experiments for preparative and analytical purposes. The system conditions can be set and monitored, e.g. temperature, its gradients and heat flux. Some special features include ( I) high heating rates up to 120 degrees C/s with

Applicability of solid-phase microextraction combined with gas chromatography atomic emission detection (GC-MIP AED) for the determination of butyltin compounds in sediment samples

Energy Technology Data Exchange (ETDEWEB)

Carpinteiro, J.; Rodriguez, I.; Cela, R. [Universidad de Santiago de Compostela, Departamento de Quimica Analitica, Nutricion y Bromatologia, Instituto de Investigacion y Analisis Alimentario, Santiago de Compostela 15782 (Spain)

2004-11-01

The performance of solid-phase microextraction (SPME) applied to the determination of butyltin compounds in sediment samples is systematically evaluated. Matrix effects and influence of blank signals on the detection limits of the method are studied in detail. The interval of linear response is also evaluated in order to assess the applicability of the method to sediments polluted with butyltin compounds over a large range of concentrations. Advantages and drawbacks of including an SPME step, instead of the classic liquid-liquid extraction of the derivatized analytes, in the determination of butyltin compounds in sediment samples are considered in terms of achieved detection limits and experimental effort. Analytes were extracted from the samples by sonication using glacial acetic acid. An aliquot of the centrifuged extract was placed on a vial where compounds were ethylated and concentrated on a PDMS fiber using the headspace mode. Determinations were carried out using GC-MIP AED. (orig.)

Amino acid analysis in biological fluids by GC-MS

OpenAIRE

Kaspar, Hannelore

2009-01-01

Amino acids are intermediates in cellular metabolism and their quantitative analysis plays an important role in disease diagnostics. A gas chromatography-mass spectrometry (GC-MS) based method was developed for the quantitative analysis of free amino acids as their propyl chloroformate derivatives in biological fluids. Derivatization with propyl chloroformate could be carried out directly in the biological samples without prior protein precipitation or solid-phase extraction of the amino acid...

GC-FID coupled with chemometrics for quantitative and chemical fingerprinting analysis of Alpinia oxyphylla oil.

Science.gov (United States)

Miao, Qing; Kong, Weijun; Zhao, Xiangsheng; Yang, Shihai; Yang, Meihua

2015-01-01

Analytical methods for quantitative analysis and chemical fingerprinting of volatile oils from Alpinia oxyphylla were established. The volatile oils were prepared by hydrodistillation, and the yields were between 0.82% and 1.33%. The developed gas chromatography-flame ionization detection (GC-FID) method showed good specificity, linearity, reproducibility, stability and recovery, and could be used satisfactorily for quantitative analysis. The results showed that the volatile oils contained 2.31-77.30 μL/mL p-cymene and 12.38-99.34 mg/mL nootkatone. A GC-FID fingerprinting method was established, and the profiles were analyzed using chemometrics. GC-MS was used to identify the principal compounds in the GC-FID profiles. The profiles of almost all the samples were consistent and stable. The harvesting time and source were major factors that affected the profile, while the volatile oil yield and the nootkatone content had minor secondary effects. Copyright © 2014 Elsevier B.V. All rights reserved.

TOXICOLOGICAL DRUG SCREENING BY GC-MS VERSUS HPLC-DAD USING A COMMON EFFICIENT EXTRACTION PROCEDURE SCREENING TOXICOLOGIQUE DES MEDICAMENTS PAR HPLC-DAD ET GC-MS: PROTOCOLE D’EXTRACTION UNIQUE

Directory of Open Access Journals (Sweden)

SELOUA ELMRABEH

2015-05-01

Full Text Available This paper presents a common extraction method for toxicological drug screening by gas chromatography-mass spectrometry (GC-MS and high-performance liquid chromatography with diode-array detection (HPLC-DAD. Liquid-liquid extraction was performed using plasma of 104 samples at the Laboratory of Moroccan Poison Control and Pharmacovigilance Center during a period of 12 months. The results obtained by HPLC-DAD are compared with those determined with GC-MS. 76 cases (73.08 % were found positive for at least by one of these two techniques. HPLC-DAD identified 59.87 % of all positive results, and 10 molecules were identified only by HPLC-DAD. GC/MS identified 40.13 % of all positives, and 4 molecules were identified only by GC/MS. In order to evaluate the performance of this extraction method, an extraction yield was calculated for three classes of drugs. All the analyzed molecules were obtained in satisfactory yields (higher than 50 % except for carbamazepine, amitriptyline and nortriptyline. Overall, the results indicate that the extraction method is well adapted for toxicological drug screening. The use of common extraction simultaneously for the two techniques can reduce workload and costs of screening, while increasing the validity and reliability of the results.

Functional characterization of two CITED3 homologs (gcCITED3a and gcCITED3b in the hypoxia-tolerant grass carp, Ctenopharyngodon idellus

Directory of Open Access Journals (Sweden)

Yu Richard MK

2009-11-01

Full Text Available Abstract Background CITED proteins belong to a family of non-DNA-binding transcriptional co-regulators that are characterized by a conserved ED-rich domain at the C-terminus. This family of genes is involved in the regulation of a variety of transcriptional responses through interactions with the CBP/p300 integrators and various transcription factors. In fish, very little is known about the expression and functions of CITEDs. Results We have characterized two closely related but distinct CITED3 genes, gcCited3a and gcCited3b, from the hypoxia-tolerant grass carp. The deduced gcCITED3a and gcCITED3b proteins share 72% amino acid identity, and are highly similar to the CITED3 proteins of both chicken and Xenopus. Northern blot analysis indicates that the mRNA expression of gcCited3a and gcCited3b is strongly induced by hypoxia in the kidney and liver, respectively. Luciferase reporter assays demonstrated that both gene promoters are activated by gcHIF-1. Further, ChIP assays comparing normal and hypoxic conditions reveal differential in vivo binding of gcHIF-1 to both gene promoters in kidney and liver tissues. HRE-luciferase reporter assays demonstrated that both gcCITED3a and gcCITED3b proteins inhibit gcHIF-1 transcriptional activity, and GST pull-down assays confirmed that both proteins bind specifically to the CH1 domain of the grass carp p300 protein. Conclusion The grass carp gcCITED3a and gcCITED3b genes are differentially expressed and regulated in different fish organs in response to hypoxic stress. This is the first report demonstrating in vivo regulation of two closely-related CITED3 isogenes by HIF-1, as well as CITED3 regulation of HIF-1 transcriptional activity in fish. Overall, our findings suggest that unique molecular mechanisms operate through these two gcCITED3 isoforms that likely play an important regulatory role in the hypoxic response in the grass carp.

At least two Fc Neu5Gc residues of monoclonal antibodies are required for binding to anti-Neu5Gc antibody

OpenAIRE

Yu, Chuanfei; Gao, Kai; Zhu, Lei; Wang, Wenbo; Wang, Lan; Zhang, Feng; Liu, Chunyu; Li, Meng; Wormald, Mark R.; Rudd, Pauline M.; Wang, Junzhi

2016-01-01

Two non-human glycan epitopes, galactose-Į-1,3-galactose (Į-gal) and Neu5Gc-Į-2-6-galactose (Neu5Gc) have been shown to be antigenic when attached to Fab oligosaccharides of monoclonal antibodies (mAbs) , while Į-gal attached to Fc glycans were not. However, the antigenicity of Neu5Gc on the Fc glycans remains unclear in the context that most mAbs carry only Fc glycans. After studying two clinical mAbs carrying significant amounts of Fc Neu5Gc, we show that their binding activity with anti-Ne...

Determination of patulin in fruit juices using HPLC-DAD and GC-MSD techniques.

Science.gov (United States)

Moukas, Athanasios; Panagiotopoulou, Vasiliki; Markaki, Panagiota

2008-08-15

A high performance liquid chromatography with a diode-array detector (HPLC-DAD) and a gas chromatography with a mass spectrometer (GC-MSD) are described for the determination of patulin (PAT) in apple juice. The limits of detection (DL) and quantification (QL) for the HPLC-DAD and GC-MSD method were found to be (DL=0.23μgkg(-1) QL=1.2μgkg(-1)) and (DL=5.8μgkg(-1) and QL=13.8μgkg(-1)), respectively. The recovery factors for HPLC-DAD and GC-MSD were found to be 99.5% (RSD%=0.73) and 41% (RSD%=10.03), respectively. The HPLC-DAD method was used to determine the occurrence of PAT in 90 samples of fruit juices. Results revealed the presence of PAT in 100% of the samples examined. The mean values of PAT in concentrated fruit juices and in the commercial fruit juices collected from the Greek market were found to be 10.54μg PAT kg(-1) and 5.57μg PAT kg(-1) juice, respectively. The most contaminated samples were four concentrated juices ranging from 18.10μg PAT kg(-1) to 36.8μg PAT kg(-1) juice. The daily exposure to patulin for the consumers of all ages in Greece, is ranging from 0.008μg PAT kg(-1) bw to 0.1μg PAT kg(-1) bw if the daily intake of fruit juices is from 0.1 to 0.5kg. With the exception to the most contaminated sample, the daily exposure due to the samples examined, is below the provisional maximum tolerable daily intake for PAT (0.4μg PAT kg(-1) bw). Copyright © 2008 Elsevier Ltd. All rights reserved.

Detection and quantification of ochratoxin A and deoxynivalenol in barley grains by GC-MS and electronic nose.

Science.gov (United States)

Olsson, J; Börjesson, T; Lundstedt, T; Schnürer, J

2002-02-05

Mycotoxin contamination of cereal grains can be detected and quantified using complex extraction procedures and analytical techniques. Normally, the grain odour, i.e. the presence of non-grain volatile metabolites, is used for quality classification of grain. We have investigated the possibility of using fungal volatile metabolites as indicators of mycotoxins in grain. Ten barley samples with normal odour, and 30 with some kind of off-odour were selected from Swedish granaries. The samples were evaluated with regard to moisture content, fungal contamination, ergosterol content, and levels of ochratoxin A (OA) and deoxynivalenol (DON). Volatile compounds were also analysed using both an electronic nose and gas chromatography combined with mass spectrometry (GC-MS). Samples with normal odour had no detectable ochratoxin A and average DON contents of 16 microg kg(-1) (range 0-80), while samples with off-odour had average OA contents of 76 microg kg(-1) (range 0-934) and DON contents of 69 microg kg(-1) (range 0-857). Data were evaluated by multivariate data analysis using projection methods such as principal component analysis (PCA) and partial least squares (PLS). The results show that it was possible to classify the OA level as below or above the maximum limit of 5 microg kg(-1) cereal grain established by the Swedish National Food Administration, and that the DON level could be estimated using PLS. Samples with OA levels below 5 microg kg(-1) had higher concentration of aldehydes (nonanal, 2-hexenal) and alcohols (1-penten-3-ol, 1-octanol). Samples with OA levels above 5 microg kg(-1) had higher concentrations of ketones (2-hexanone, 3-octanone). The GC-MS system predicted OA concentrations with a higher accuracy than the electronic nose, since the GC-MS misclassified only 3 of 37 samples and the electronic nose 7 of 37 samples. No correlation was found between odour and OA level, as samples with pronounced or strong off-odours had OA levels both below and above 5

The glycosylation and characterization of the candidate Gc macrophage activating factor

DEFF Research Database (Denmark)

Ravnsborg, Tina; Olsen, Dorthe T; Thysen, Anna Hammerich

2010-01-01

The vitamin D binding protein, Gc globulin, has in recent years received some attention for its role as precursor for the extremely potent macrophage activating factor (GcMAF). An O-linked trisaccharide has been allocated to the threonine residue at position 420 in two of the three most common...... isoforms of Gc globulin (Gc1s and Gc1f). A substitution for a lysine residue at position 420 in Gc2 prevents this isoform from being glycosylated at that position. It has been suggested that Gc globulin subjected sequentially to sialidase and galactosidase treatment generates GcMAF in the form of Gc...... globulin with only a single GalNAc attached to T420. In this study we confirm the location of a linear trisaccharide on T420. Furthermore, we provide the first structural evidence of the generation of the proposed GcMAF by use of glycosidase treatment and mass spectrometry. Additionally the generated GcMAF...

Cannabinoids determination in oral fluid by SPME-GC/MS and UHPLC-MS/MS and its application on suspected drivers.

Science.gov (United States)

Anzillotti, Luca; Castrignanò, Erika; Strano Rossi, Sabina; Chiarotti, Marcello

2014-12-01

The confirmation of Δ9-tetrahydrocannabinol (THC) in oral fluid (OF) is an important issue for assessing Driving Under the Influence of Drugs (DUID). The aim of this research was to develop a highly sensitive method with minimal sample pre-treatment suitable for the analysis of small OF volumes (100 μL) for the confirmation of cannabinoids in DUID cases. Two methods were compared for the confirmation of THC in residual OF samples, obtained from a preliminary on-site screening with commercial devices. An ultra high performance LC-MS (UHPLC-MS/MS) method and an SPME-GC/MS method were hence developed. 100 μL of the residual mixture OF/preservative buffer or neat OF was simply added to 10 μL of THC-D3 (1 μg/mL) and submitted to the two different analyses: A - direct injection of 10 μL in UHPLC-MS/MS in positive electrospray ionisation (ESI) mode and B - sampling for 30 min with SPME (100 μm polydimethylsiloxane or PDMS fibre) and direct injection by desorption of the fibre in the GC injection port. The lowest limit of detection (LLOD) of THC was 2 ng/mL in UHPLC-MS/MS and 0.5 ng/mL in SPME-GC/MS. In addition, cannabidiol (CBD) and cannabinol (CBN) could be detected in GC/MS equipment at 2 ng/mL, whilst in UHPLC-MS/MS the LLOD was 20 ng/mL. Both methods were applied to 70 samples coming from roadside tests. By SPME-GC/MS analysis, THC was confirmed in 42 samples, whilst CBD was detected in 21 of them, along with CBN in 14 samples. THC concentrations ranged from traces below the lowest limit of quantification or LLOQ (2 ng/mL) up to 690 ng/mL. Copyright © 2014 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.

A simple method for assessment of human anti-Neu5Gc antibodies applied to Kawasaki disease.

Directory of Open Access Journals (Sweden)

Vered Padler-Karavani

Full Text Available N-glycolylneuraminic acid (Neu5Gc is an immunogenic sugar of dietary origin that metabolically incorporates into diverse native glycoconjugates in humans. Anti-Neu5Gc antibodies are detected in all human sera, though with variable levels and epitope-recognition profiles. These antibodies likely play a role in several inflammation-mediated pathologies including cardiovascular diseases and cancer. In cancer, they have dualistic and opposing roles, either stimulating or repressing disease, as a function of their dose, and some of these antibodies serve as carcinoma biomarkers. Thus, anti-Neu5Gc antibodies may signify risk of inflammation-mediated diseases, and changes in their levels could potentially be used to monitor disease progression and/or response to therapy. Currently, it is difficult to determine levels of anti-Neu5Gc antibodies in individual human samples because these antibodies recognize multiple Neu5Gc-epitopes. Here we describe a simple and specific method for detection and overall estimation of human anti-Neu5Gc antibodies. We exploit the difference between two mouse models that differ only by Neu5Gc-presence (wild-type or Neu5Gc-absence (Cmah(-/- knockout. We characterize mouse serum from both strains by HPLC, lectin and mass-spectrometry analysis and show the target Neu5Gc-epitopes. We then use Cmah(-/- knockout sera to inhibit all non-Neu5Gc-reactivity followed by binding to wild-type sera to detect overall anti-Neu5Gc response in a single assay. We applied this methodology to characterize and quantify anti-Neu5Gc IgG and IgA in sera of patients with Kawasaki disease (KD at various stages compared to controls. KD is an acute childhood febrile disease characterized by inflammation of coronary arteries that untreated may lead to coronary artery aneurysms with risk of thrombosis and myocardial infarction. This estimated response is comparable to the average of detailed anti-Neu5Gc IgG profile analyzed by a sialoglycan microarray

Detection Characteristics of Gamma-Irradiated Seeds by using PSL, TL, ESR and GC/MS

International Nuclear Information System (INIS)

Kim, K.H.; Shon, J.H.; Kang, Y.J.; Jo, T.Y.; Park, H.Y.; Kwak, J.Y.; Lee, J.H.; Park, Y.C.; Kim, J.I.; Lee, H.J.; Lee, S.J.; Han, S.B.

2013-01-01

In this study, we investigated the applicability of the photostimulated luminescence (PSL), thermoluminescence (TL), electron spin resonance (ESR) and gas chromatography/mass spectrometry (GC/MS) methods for 5 seeds which are not allowed to be irradiated in Korea. All 5 seeds including evening primrose seed, safflower seed, rape seed, sunflower seed and flax seed were analyzed. Samples were irradiated at 1~10 kGy using a 60 Co gamma-ray irradiator. In PSL study, the photon counts of all the unirradiated samples showed negative (lower than 700). The photon counts of irradiated (1, 5, 10 kGy) samples showed positive (higher than 5,000). In TL analysis, results showed that it is possible to apply TL method to all foods containing minerals. In ESR measurements, the ESR signal (single-line) intensity of irradiated foods was higher than non-irradiated foods. The hydrocarbons 1,7-hexadecadiene (C 16:2 ) and 8-heptadecene (C 17:1 ) from oleic acid were detected only in the irradiated samples before and after the treatment at doses ≥ 1 kGy, but they were not detected in non-irradiated samples before and after treatment. These two hydrocarbons could be used as markers to identify irradiated safflower seed, rape seed, Sunflower seed and flax seed. And then, the hydrocarbons 1,7,10-hexadecatriene (C 16:3 ) and 6,9-heptadecadiene (C 17:2 ) from linoleic acid were detected in the evening primrose seed, safflower seed and sunflower seed. According to the results, PSL, TL and GC/ MS methods were successfully applied to detect the irradiated foods. It is concluded that PSL, TL and GC/MS methods are suitable for detection of irradiated samples and a combined method is recommendable for enhancing the reliability of detection results. (author)

Validation of rapid dioxin screening by GC-FID in fish products

Energy Technology Data Exchange (ETDEWEB)

Bassompierre, M.; Munck, L.; Bro, R.; Tomasi, G.; Engelsen, S.B. [Royal Veterinary and Agricultural Univ., Copenhagen (Denmark). Food Technology, Institute of Food Science, Centre for Advanced Food Studies

2004-09-15

A novel, cost- and time-effective dioxin screening method was developed and validated for fish product. The method is based on multivariate covariance between fatty acid composition monitored by GC-FID and dioxin content as teq WHO pg/ g fat. A dioxin range varying from 1.1 to 47.1 pg TEQ-WHO/ g fat using 65 fish meal samples was accessible for model calibration. An optimal multivariate dioxin prediction model was developed based on automatic peak integration, thereby enabling extraction of the area of 140 peaks from the gas chromatogramms. Models were produced employing partial least squares regression (PLS) based upon the duplicate GC-FID run and 46 specific peaks, selected after variable selection from the 140 investigated. The best results were yielded by local pls modelling employing three latent variables based upon the 12 nearest neighbors. For each prediction sample, the neighbors, yielding the 12 smallest sum of squares of differences to the test sample using the 140 peaks, were extracted from the whole calibration set and a local model built using these 12 chromatograms and related dioxin content. Prediction performance was thereafter validated for 10 fully independent samples. The performance of this model, yielded a correlation of 0.85 (r{sup 2}) and a root mean square error of prediction of 2.3 pg PCDD/F TEQWHO/ g fat.

Steroids from Poison Hemlock (Conium maculatum L.: A GC-MS analysis

Directory of Open Access Journals (Sweden)

Radulović Niko S.

2011-01-01

Full Text Available The steroid content of Conium maculatum L. (Poison Hemlock, Apiaceae, a well-known weed plant species, was studied herein for the first time. This was achieved by detailed GC-MS analyses of twenty two samples (dichloromethane extracts of different plant organs of C. maculatum at three or four different stages of phenological development, collected from three locations. In total, twenty four different steroids were identified. Six steroids had an ergostane nucleus while the other ones possessed a stigmastane carbon framework. The identity of these compounds was determined by spectral means (MS fragmentation, GC co-injections with authentic standards and chemical transformation (silylation. Steroid compounds were noted to be the main chemical constituents of root extracts (up to 70 % of this plant species in the last phase of development. The predominant ones were stigmasta-5,22- dien-3β-ol (stigmasterol and stigmasta-5-en-3β-ol (β-sitosterol. In an attempt to classify the samples, principal component analysis (PCA and agglomerative hierarchical clustering (AHC were performed using steroid percentages as variables.

The glycosylation and characterization of the candidate Gc macrophage activating factor.

Science.gov (United States)

Ravnsborg, Tina; Olsen, Dorthe T; Thysen, Anna Hammerich; Christiansen, Maja; Houen, Gunnar; Højrup, Peter

2010-04-01

The vitamin D binding protein, Gc globulin, has in recent years received some attention for its role as precursor for the extremely potent macrophage activating factor (GcMAF). An O-linked trisaccharide has been allocated to the threonine residue at position 420 in two of the three most common isoforms of Gc globulin (Gc1s and Gc1f). A substitution for a lysine residue at position 420 in Gc2 prevents this isoform from being glycosylated at that position. It has been suggested that Gc globulin subjected sequentially to sialidase and galactosidase treatment generates GcMAF in the form of Gc globulin with only a single GalNAc attached to T420. In this study we confirm the location of a linear trisaccharide on T420. Furthermore, we provide the first structural evidence of the generation of the proposed GcMAF by use of glycosidase treatment and mass spectrometry. Additionally the generated GcMAF candidate was tested for its effect on cytokine release from macrophages in human whole blood. Copyright 2010 Elsevier B.V. All rights reserved.

A Monolithically-Integrated μGC Chemical Sensor System

Directory of Open Access Journals (Sweden)

Davor Copic

2011-06-01

Full Text Available Gas chromatography (GC is used for organic and inorganic gas detection with a range of applications including screening for chemical warfare agents (CWA, breath analysis for diagnostics or law enforcement purposes, and air pollutants/indoor air quality monitoring of homes and commercial buildings. A field-portable, light weight, low power, rapid response, micro-gas chromatography (μGC system is essential for such applications. We describe the design, fabrication and packaging of mGC on monolithically-integrated Si dies, comprised of a preconcentrator (PC, μGC column, detector and coatings for each of these components. An important feature of our system is that the same mechanical micro resonator design is used for the PC and detector. We demonstrate system performance by detecting four different CWA simulants within 2 min. We present theoretical analyses for cost/power comparisons of monolithic versus hybrid μGC systems. We discuss thermal isolation in monolithic systems to improve overall performance. Our monolithically-integrated μGC, relative to its hybrid cousin, will afford equal or slightly lower cost, a footprint that is 1/2 to 1/3 the size and an improved resolution of 4 to 25%.

An Innovative Rapid Method for Analysis of 10 Organophosphorus Pesticide Residues in Wheat by HS-SPME-GC-FPD/MSD.

Science.gov (United States)

Du, Xin; Ren, YongLin; Beckett, Stephen J

2016-01-01

The rapid detection of pesticide residues in wheat has become a top food security priority. A solvent-free headspace solid-phase microextraction (HS-SPME) has been evaluated for rapid screening of organophosphorus pesticide (OPP) residues in wheat with high sensitivity. Individual wheat samples (1.7 g), spiked with 10 OPPs, were placed in a 4 mL sealed amber glass vial and heated at 60°C for 45 min. During this time, the OPP residues were extracted with a 50 μm/30 μm divinylbenzene (DVB)/carboxen (CAR)/plasma desorption mass spectroscopy polydimethylsiloxane (PDMS) fiber from the headspace above the sample. The fiber was then removed and injected into the GC injection port at 250°C for desorption of the extracted chemicals. The multiple residues were identified by a GC mass spectrometer detector (GC-MSD) and quantified with a GC flame photometric detector (GC-FPD). Seven spiked levels of 10 OPPs on wheat were analyzed. The GC responses for a 50 μm/30 μm DVB/CAR/PDMS fiber increased with increasing spiking levels, yielding significant (R(2) > 0.98) linear regressions. The lowest LODs of the multiple pesticide standards were evaluated under the conditions of the validation study in a range of levels from 0 (control) to 100 ng of pesticide residue per g of wheat that separated on a low-polar GC capillary column (Agilent DB-35UI). The results of the HS-SPME method were compared with the QuEChERS AOAC 2007.01 method and they showed several advantages over the latter. These included improved sensitivity, selectivity, and simplicity.

Determination of Glyphosate Levels in Breast Milk Samples from Germany by LC-MS/MS and GC-MS/MS

NARCIS (Netherlands)

Steinborn, Angelika; Alder, Lutz; Michalski, Britta; Zomer, Paul; Bendig, Paul; Martinez, Sandra Aleson; Mol, Hans G.J.; Class, Thomas J.; Costa Pinheiro, Nathalie

2016-01-01

This study describes the validation and application of two independent analytical methods for the determination of glyphosate in breast milk. They are based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS), respectively. For

Gc globulin as a diagnostic and prognostic marker in horses

DEFF Research Database (Denmark)

Pihl, Tina Holberg

can prevent development of shock and thereby increase survival chances. The in vivo toxicity of Gc-globulin infusion is currently being investigated in horses and other species. Gc-globulin has been demonstrated in horse plasma and its structure closely resembles that of human Gc-globulin. Gc......-globulin concentrations in horses under clinical conditions have never previously been investigated. The Ph.D. project focuses on Gc-globulin as a prognostic marker in horses with acute abdominal pain....

Analytical and sensorial characterization of the aroma of wines produced with sour rotten grapes using GC-O and GC-MS: identification of key aroma compounds.

Science.gov (United States)

Barata, André; Campo, Eva; Malfeito-Ferreira, Manuel; Loureiro, Virgílio; Cacho, Juan; Ferreira, Vicente

2011-03-23

In the present work, the aroma profiles of wines elaborated from sound and sour rot-infected grapes as raw material have been studied by sensory analysis, gas chromatography-olfactometry (GC-O), and gas chromatography-mass spectrometry (GC-MS), with the aim of determining the odor volatiles most likely associated with this disease. The effect of sour rot was tested in monovarietal wines produced with the Portuguese red grape variety Trincadeira and in blends of Cabernet Sauvignon and sour rotten Trincadeira grapes. Wines produced from damaged berries exhibited clear honey-like notes not evoked by healthy samples. Ethyl phenylacetate (EPhA) and phenylacetic acid (PAA), both exhibiting sweet honey-like aromas, emerged as key aroma compounds of sour rotten wines. Their levels were 1 order of magnitude above those found in controls and reached 304 and 1668 μg L(-1) of EPhA and PAA, respectively, well above the corresponding odor thresholds. Levels of γ-nonalactone also increased by a factor 3 in sour rot samples. Results also suggest that sour rot exerts a great effect on the secondary metabolism of yeast, decreasing the levels of volatiles related to fatty acids and amino acid synthesis. The highest levels of γ-decalactone of up to 405 μg L(-1) were also found in all of the samples, suggesting that this could be a relevant aroma compound in Trincadeira wine aroma.

A GC Instrument Simulator

Science.gov (United States)

Armitage, D. Bruce

1999-02-01

This simulator was developed to help students beginning the study of gas chromatographic instruments to understand their operation. It is not meant to teach chromatographic theory. The instrument simulator is divided into 5 sections. One is for sample preparation. Another is used to manage carrier gases and choose a detector and column. The third sets the conditions for either isothermal or programmed temperature operation. A fourth section models manual injections, and the fifth is the autosampler. The operator has a choice among 6 columns of differing diameters and packing polarities and a choice of either isothermal or simple one-stage temperature programming. The simulator can be operated in either single-sample mode or as a 10-sample autosampler. The integrator has two modes of operation, a "dumb" mode in which only the retention time, area of the peak, and percentage area are listed and a "smart" mode that also lists the components' identities. The identities are obtained from a list of names and retention times created by the operator. Without this list only the percentages and areas are listed. The percentages are based on the areas obtained from the chromatogram and not on the actual percentages assigned during sample preparation. The data files for the compounds used in the simulator are ASCII files and can be edited easily to add more compounds than the 11 included with the simulator. A maximum of 10 components can be used in any one sample. Sample mixtures can be made on a percent-by-volume basis, but not by mass of sample per volume of solvent. A maximum of 30 compounds can be present in any one file, but the number of files is limited only by the operating system. (I suggest that not more than 20 compounds be used in any one file, as scrolling through large numbers of compounds is annoying to say the least.) File construction and layout are discussed in detail in the User's Manual. Chromatograms are generated by calculating a retention time based on

Protocols for the measurement of the F2-isoprostane, 15(S)-8-iso-prostaglandin F2α, in biological samples by GC-MS or GC-MS/MS coupled with immunoaffinity column chromatography.

Science.gov (United States)

Tsikas, Dimitrios; Suchy, Maria-Theresia

2016-04-15

Arachidonic acid, the origin of the eicosanoids family, occurs in biological samples as free acid and as ester in lipids. Free arachidonic acid is oxidized to numerous metabolites by means of enzymes including cyclooxygenase (COX). Arachidonic acid esterified to lipids is attacked by reactive oxygen species (ROS) to generate numerous oxidized arachidonic acid derivatives. Generally, it is assumed that ROS-derived arachidonic acid derivatives are distinct from those generated by enzymes such as COX. Therefore, ROS-generated eicosanoids are considered specific biomarkers of oxidative stress. However, there are serious doubts concerning a strict distinction between the enzyme-derived eicosanoids and the ROS-derived iso-eicosanoids. Prominent examples are prostaglandin F2α (PGF2α) and 15(S)-8-iso-prostaglandin F2α (15(S)-8-iso-PGF2α) which have been originally considered to exclusively derive from COX and ROS, respectively. There is convincing evidence that both COX and ROS can oxidize arachidonic acid to PGF2α and 15(S)-8-iso-PGF2α. Thus, many results previously reported for 15(S)-8-iso-PGF2α as exclusive ROS-dependent reaction product, and consequently as a specific biomarker of oxidative stress, require a careful re-examination which should also consider the analytical methods used to measure 15(S)-8-iso-PGF2α. This prominent but certainly not the only example underlines more than ever the importance of the analytical chemistry in basic and clinical research areas of oxidative stress. In the present work, we report analytical protocols for the reliable quantitative determination of 15(S)-8-iso-PGF2α in human biological samples including plasma and urine by mass spectrometry coupled to gas chromatography (GC-MS, GC-MS/MS) after specific isolation of endogenous 15(S)-8-iso-PGF2α and the externally added internal standard [3,3',4,4'-(2)H4]-15(S)-8-iso-PGF2α by immunoaffinity column chromatography (IAC). 15(S)-8-iso-PGF2α esterified to plasma lipids is

Molecular analysis of intact preen waxes of Calidris Canutus (Aves: Scolopacidae) by GC/MS and GC/MS/MS

NARCIS (Netherlands)

Sinninghe Damsté, J.S.; Dekker, M.H.A.; Piersma, T.

2000-01-01

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

Improvement of the inlet system for the spray-jet technique for use in spectroscopic studies and molecular deposition

International Nuclear Information System (INIS)

Yamada, Toshiki; Shinohara, Hidenori; Mashiko, Shinro

2006-01-01

We previously developed a molecular beam apparatus with a spray-jet technique in order to produce a molecular beam of non-volatile molecules in vacuum from the sprayed mist of a sample solution. The apparatus is for use in spectroscopic studies or a means of molecular deposition. The spray-jet inlet system consisted of an ultrasonic nebulizer, an inlet chamber and a pulsed nozzle. In the present paper, further improvements to the spray-jet inlet system are reported. The main improvement is the introduction of a pneumatic nebulizer to replace the previous ultrasonic nebulizer. The efficiency of molecular beam generation was evaluated on the basis of the signal intensity of the resonantly enhanced multiphoton ionization time-of-flight mass (REMPI-TOFMS) spectra for a Rhodamine B/methanol solution and the amount of sample consumed. The introduction of the pneumatic nebulizer increased the efficiency by a factor of 20

Comparative evaluation of ICP sample introduction systems to be used in the metabolite profiling of chlorine-containing pharmaceuticals via HPLC-ICP-MS.

Science.gov (United States)

Klencsár, Balázs; Sánchez, Carlos; Balcaen, Lieve; Todolí, José; Lynen, Frederic; Vanhaecke, Frank

2018-05-10

A systematic evaluation of four different ICP sample introduction systems to be used in the context of metabolite profiling of chlorine-containing pharmaceuticals via HPLC-ICP-MS was carried out using diclofenac and its major metabolite, 4'-hydroxy-diclofenac, as model compounds. The strict requirements for GMP validation of chromatographic methods in the pharmaceutical industry were adhered to in this context. The final aim of this investigation is an extension of the applicability and validatability of HPLC-ICP-MS in the field of pharmaceutical R&D. Five different gradient programmes were tested while the baseline peak width (w b ), peak capacity (P), USP tailing factor (A s ) and USP signal-to-noise ratio (USP S/N) were determined as major indicators of the chromatographic performance and the values obtained were compared to the corresponding FDA recommendations (if applicable). Four different ICP-MS sample introductions systems were investigated involving two units typically working at higher flow rates (∼1.0 mL min -1 ) and another two systems working at lower flow rates (∼0.1 mL min -1 ). Optimal conditions with potential for applicability under GMP conditions were found at a mobile phase flow rate of 1.0 mL min -1 by using a pneumatic micro-flow LC nebulizer mounted onto a Peltier-cooled cyclonic spray chamber cooled to -1 °C for sample introduction. Under these conditions, HPLC-ICP-MS provided a chromatographic performance similar to that of HPLC with UV detection. The peak shape (USP tailing factor = 1.1-1.4) was significantly improved compared to that obtained with the Peltier-cooled Scott-type spray chamber. Two alternative sample introduction systems - a POINT ® and a High-Temperature Torch-Integrated Sample Introduction System (hTISIS) - were also tested at a flow rate of 0.1 mL min -1 using a chromatographic column with 1.0 mm ID. Although these systems allowed the peak shape to be improved compared to that obtained with

Comparison of high sensitivity analytical methods (PTR-MS, MIMS, GC-O, SA) and application to food chemistry

International Nuclear Information System (INIS)

Boscaini, E.

2002-10-01

Application of PTR-MS to flavor analysis and the development of the membrane introduction proton-transfer-reaction-mass-spectrometry are the main topics of this thesis. The results of classical sensory analysis and of PTR-MS analysis are compared in defining flavor profiles of 7 different brands of mozzarella cheese. The PTR-MS mass spectra of the headspace of mozzarella held at 36 o C are compared to the judge panel flavor profile. Multivariate statistical data analysis shows that the two methods perform comparable sample discrimination. This shows that PTR-MS is a very promising method for the instrumental evaluation of the flavour sensory profile of food, opening new opportunities both in the control of quality and technological processes, as well as in the fundamental comprehension of the physiological processes of aroma perception. In the same chapter is also described a method for the identification of the masses of a mass spectra obtained with PTR-MS. Although the identification is always tentative, it might suggest which substances play an important role in the classification of different products. I.e. mass 45 and 47 associated to acetaldehyde and ethanol respectively reveal a higher fermentation activity in product B than G, as expected due to their manufacture processes. Gas Chromatography-Olfactometry (GC-O) and Proton Transfer Reaction-Mass Spectrometry (PTR-MS) techniques were used to define odor active and volatile profile of three grana cheeses: Grana Padano (GP), Parmigiano Reggiano (PR) and Grana Trentino (GT). Samples for GC-O analysis were prepared by dynamic headspace extraction while a direct analysis of the headspace formed over cheese was performed by PTR-MS. Major contribution to the odor profile was given by ethyl butanoate, 2-heptanone and ethyl hexanoate with fruity notes. High concentration of mass 45 tentatively identified with acetaldehyde was found by PTR-MS analysis. Low odor threshold compounds e.g. methional and 1-octen-3-one

Characterization of ion processes in a GC/DMS air quality monitor by integration of the instrument to a mass spectrometer.

Science.gov (United States)

Limero, T F; Nazarov, E G; Menlyadiev, M; Eiceman, G A

2015-02-07

The air quality monitor (AQM), which included a portable gas chromatograph (GC) and a detector was interfaced to a mass spectrometer (MS) by introducing flow from the GC detector to the atmospheric pressure ion source of the MS. This small GC system, with a gas recirculation loop for carrier and detector make-up gases, comprised an inlet to preconcentrate volatile organic compounds (VOCs) in air, a thermal desorber before the GC column, a differential mobility spectrometer (DMS), and another DMS as an atmospheric pressure ionization source for the MS. Return flow to the internally recirculated air system of the AQM's DMS was replenished using purified air. Although ions and unreacted neutral vapors flowed from the detector through Viton® tubing into the source of the MS, ions were not detected in the MS without the auxillary ion source, (63)Ni as in the mobility detector. The GC-DMS-MS instrument provided a 3-D measurement platform (GC, DMS, and MS analysis) to explore the gas composition inside the GC-DMS recirculation loop and provide DMS-MS measurement of the components of a complex VOC mixture with performance significantly enhanced by mass-analysis, either with mass spectral scans or with an extracted ion chromatogram. This combination of a mobility spectrometer and a mass spectrometer was possible as vapors and ions are carried together through the DMS analyzer, thereby preserving the chromatographic separation efficiency. The critical benefit of this instrument concept is that all flows in and through the thoroughly integrated GC-DMS analyzer are kept intact allowing a full measure of the ion and vapor composition in the complete system. Performance has been evaluated using a synthetic air sample and a sample of airborne vapors in a laboratory. Capabilities and performance values are described using results from AQM-MS analysis of purified air, ambient air from a research laboratory in a chemistry building, and a sample of synthetic air of known composition

Ultra high performance liquid chromatography with ion-trap TOF-MS for the fast characterization of flavonoids in Citrus bergamia juice.

Science.gov (United States)

Sommella, Eduardo; Pepe, Giacomo; Pagano, Francesco; Tenore, Gian Carlo; Dugo, Paola; Manfra, Michele; Campiglia, Pietro

2013-10-01

We have developed a fast ultra HPLC with ion-trap TOF-MS method for the analysis of flavonoids in Citrus bergamia juice. With respect to the typical methods for the analysis of these matrices based on conventional HPLC techniques, a tenfold faster separation was attained. The use of a core-shell particle column ensured high resolution within the fast analysis time of only 5 min. Unambiguous determination of flavonoid identity was obtained by the employment of a hybrid ion-trap TOF mass spectrometer with high mass accuracy (average error 1.69 ppm). The system showed good retention time and peak area repeatability, with maximum RSD% values of 0.36 and 3.86, respectively, as well as good linearity (R(2) ≥ 0.99). Our results show that ultra HPLC can be a useful tool for ultra fast qualitative/quantitative analysis of flavonoid compounds in citrus fruit juices. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gc protein-derived macrophage-activating factor (GcMAF) stimulates cAMP formation in human mononuclear cells and inhibits angiogenesis in chick embryo chorionallantoic membrane assay.

Science.gov (United States)

Pacini, Stefania; Morucci, Gabriele; Punzi, Tiziana; Gulisano, Massimo; Ruggiero, Marco

2011-04-01

The effects of Gc protein-derived macrophage-activating factor (GcMAF) have been studied in cancer and other conditions where angiogenesis is deregulated. In this study, we demonstrate for the first time that the mitogenic response of human peripheral blood mononuclear cells (PBMCs) to GcMAF was associated with 3'-5'-cyclic adenosine monophosphate (cAMP) formation. The effect was dose dependent, and maximal stimulation was achieved using 0.1 ng/ml. Heparin inhibited the stimulatory effect of GcMAF on PBMCs. In addition, we demonstrate that GcMAF (1 ng/ml) inhibited prostaglandin E(1)- and human breast cancer cell-stimulated angiogenesis in chick embryo chorionallantoic membrane (CAM) assay. Finally, we tested different GcMAF preparations on CAM, and the assay proved to be a reliable, reproducible and inexpensive method to determine the relative potencies of different preparations and their stability; we observed that storage at room temperature for 15 days decreased GcMAF potency by about 50%. These data could prove useful for upcoming clinical trials on GcMAF.

Origin Discrimination of Osmanthus fragrans var. thunbergii Flowers using GC-MS and UPLC-PDA Combined with Multivariable Analysis Methods.

Science.gov (United States)

Zhou, Fei; Zhao, Yajing; Peng, Jiyu; Jiang, Yirong; Li, Maiquan; Jiang, Yuan; Lu, Baiyi

2017-07-01

Osmanthus fragrans flowers are used as folk medicine and additives for teas, beverages and foods. The metabolites of O. fragrans flowers from different geographical origins were inconsistent in some extent. Chromatography and mass spectrometry combined with multivariable analysis methods provides an approach for discriminating the origin of O. fragrans flowers. To discriminate the Osmanthus fragrans var. thunbergii flowers from different origins with the identified metabolites. GC-MS and UPLC-PDA were conducted to analyse the metabolites in O. fragrans var. thunbergii flowers (in total 150 samples). Principal component analysis (PCA), soft independent modelling of class analogy analysis (SIMCA) and random forest (RF) analysis were applied to group the GC-MS and UPLC-PDA data. GC-MS identified 32 compounds common to all samples while UPLC-PDA/QTOF-MS identified 16 common compounds. PCA of the UPLC-PDA data generated a better clustering than PCA of the GC-MS data. Ten metabolites (six from GC-MS and four from UPLC-PDA) were selected as effective compounds for discrimination by PCA loadings. SIMCA and RF analysis were used to build classification models, and the RF model, based on the four effective compounds (caffeic acid derivative, acteoside, ligustroside and compound 15), yielded better results with the classification rate of 100% in the calibration set and 97.8% in the prediction set. GC-MS and UPLC-PDA combined with multivariable analysis methods can discriminate the origin of Osmanthus fragrans var. thunbergii flowers. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Comprehensive two-dimensional gas chromatography for fast characterization of oil contamination

International Nuclear Information System (INIS)

Van De Weghe, H.; Vanermen, G.; Gemoets, J.; Lookman, R.; Bertels, D.

2005-01-01

coupled to a mass spectrometer. However, the peaks eluting from the second dimension column are very narrow (typically 100-200 ms) and only a time-of-flight MS (TOFMS) can deliver the high acquisition rates necessary for quantitative description of the peaks. In the present study comprehensive GC was evaluated as a tool for fast oil characterization in the context of soil remediation projects. For this routine application TOFMS was considered too expensive, and therefore a method was developed based on GCXGC/FID. The method was applied to oil-polluted soil samples and the results were compared with the TPH method. Only the extractable petroleum hydrocarbons (from n-C8 to n-C40) were quantitatively analyzed. Compared with the TPH method, the major advantage of GCXGC is that a more detailed chemical description of the oil pollution is obtained. The method is not limited to 'mineral' oil but can be applied to different types of pollution, including polar components

Comprehensive two-dimensional gas chromatography for fast characterization of oil contamination

Energy Technology Data Exchange (ETDEWEB)

Van De Weghe, H.; Vanermen, G.; Gemoets, J.; Lookman, R.; Bertels, D. [VITO, Mol (Belgium)

2005-07-01

can be coupled to a mass spectrometer. However, the peaks eluting from the second dimension column are very narrow (typically 100-200 ms) and only a time-of-flight MS (TOFMS) can deliver the high acquisition rates necessary for quantitative description of the peaks. In the present study comprehensive GC was evaluated as a tool for fast oil characterization in the context of soil remediation projects. For this routine application TOFMS was considered too expensive, and therefore a method was developed based on GCXGC/FID. The method was applied to oil-polluted soil samples and the results were compared with the TPH method. Only the extractable petroleum hydrocarbons (from n-C8 to n-C40) were quantitatively analyzed. Compared with the TPH method, the major advantage of GCXGC is that a more detailed chemical description of the oil pollution is obtained. The method is not limited to 'mineral' oil but can be applied to different types of pollution, including polar components.

Short torch design for direct liquid sample introduction using conventional and micro-nebulizers for plasma spectrometry

Science.gov (United States)

Montaser, Akbar [Potomac, MD; Westphal, Craig S [Landenberg, PA; Kahen, Kaveh [Montgomery Village, MD; Rutkowski, William F [Arlington, VA

2008-01-08

An apparatus and method for providing direct liquid sample introduction using a nebulizer are provided. The apparatus and method include a short torch having an inner tube and an outer tube, and an elongated adapter having a cavity for receiving the nebulizer and positioning a nozzle tip of the nebulizer a predetermined distance from a tip of the outer tube of the short torch. The predetermined distance is preferably about 2-5 mm.

Determination of Glycol Ethers in Ambient Air by Adsorption Sampling and Thermal Desorption with GC/MS Analysis: Performance Evaluation and Field Application

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Young-Kyo Seo

2012-01-01

Full Text Available Some of glycol ethers, such as 2-methoxyethanol (2-ME and 2-ethoxyethanol (2-EE are known to be toxic and classified as hazardous air pollutants in USA, Japan and Germany. In Korea, however, there has been no study conducted so far for these compounds in ambient air. In addition, no clear methodologies for the measurement of glycol ethers have been yet established. We carried out this study to evaluate a sampling and analytical method for the determination of glycol ethers, in ambient air samples collected in specific industrial areas of South Korea. To measure glycol ethers, adsorption sampling and thermal desorption with GC/MS analysis were used in this study. The analytical method showed good repeatability, linearity and sensitivity. The lower detection limits were estimated to be approximately 0.3∼0.5 ppb. Based on storage tests, it was suggested that samples should be analyzed within two weeks. It was also demonstrated that this method can be used for the simultaneous measurement of glycol ethers and other aromatic VOCs such as benzene, toluene, and xylenes. Field sampling campaign was carried out at 2 sites, located in a large industrial area, from October 2006 to June 2007, and a total of 480 samples were collected seasonally. Among them, 2-ME was not detected from any samples, while 2-EE and 2-Ethyloxyethylacetate (2-EEA were found in 7 and 70 samples, respectively. The measured concentrations of 2-EE and 2-EEA for samples were ranged from 0.7-2.5 ppb and from 0.5-10.5 ppb, respectively. To our knowledge, this is the first measurement report for glycol ethers in the ambient atmosphere not only in Korea but also the rest of the world.

Improved Separation of Complex Polycyclic Aromatic Hydrocarbon Mixtures Using Novel Column Combinations in GC×GC/ToF-MS

Science.gov (United States)

Manzano, Carlos; Hoh, Eunha; Simonich, Staci L. Massey

2012-01-01

Complex mixtures of polycyclic aromatic hydrocarbons (PAHs) are difficult to resolve because of the high degree of overlap in compound vapor pressures, boiling points and mass spectral fragmentation patterns. The objective of this research was to improve the separation of complex PAH mixtures (including 97 different parent, alkyl-, nitro-, oxy-, thio-, chloro-, bromo-, and high molecular weight PAHs) using GC×GC/ToF-MS by maximizing the orthogonality of different GC column combinations and improving the separation of PAHs from the sample matrix interferences, including unresolved complex mixtures (UCM). Four different combinations of non-polar, polar, liquid crystal and nano-stationary phase columns were tested. Each column combination was optimized and evaluated for orthogonality using a method based on conditional entropy that considers the quantitative peak distribution in the entire two-dimensional space. Finally, an atmospheric particulate matter with diameter column in the first dimension and a 1.2 m × 0.10 mm × 0.10 µm NSP-35 nano-stationary phase column in the second dimension. In addition, the use of this column combination in GC×GC/ToF-MS resulted in significantly shorter analysis times (176 min) for complex PAH mixtures compared to one-dimensional GC/MS (257 min), as well as potentially reduced sample preparation time. PMID:22769970

Development of an interface for directly coupled solid-phase extraction and GC-MS analysis

NARCIS (Netherlands)

Öllers, M.J.H.; van Lieshout, H.P.M.; Janssen, J.G.M.; Cramers, C.A.M.G.

Solid-phase extraction (SPE) is widely used as a sample preparation technique in numerous application areas of chromatography. Large-volume injection is an attractive technique for coupling SPE to gas chromatography (GC) because it provides improved detection limits and circumvents the need for

SPE-GC/FTD determination of N-methyl-2-pyrrolidone and its metabolites in urine.

Science.gov (United States)

Kubota, Ryuichi; Endo, Yoko; Takeuchi, Akito; Inoue, Yoshinori; Ogata, Hiroko; Ogawa, Masanori; Nakagawa, Tomoo; Onda, Nobuhiko; Endo, Ginji

2007-07-01

An analytical method using a combination of solid-phase extraction (SPE) and gas chromatography with a flame thermionic detector (GC/FTD) was developed for determination of N-methyl-2-pyrrolidone (NMP), N-methylsuccinimide (MSI), and 2-hydroxy-N-methylsuccinimide (2-HMSI) in human urine. The SPE cartridge of poly(divinylbenzene/hydroxymethacrylate) used was directly loaded with urine sample, followed by elution with methyl isobutyl ketone (MIBK) and subsequent centrifugation, and the supernatant was injected into the capillary GC using a DB1701. This method allowed efficient separation of NMP, MSI, and 2-HMSI, which were nearly free of interference by other GC peaks arising from urine. Recoveries of NMP, MSI, and 2-HMSI from the SPE cartridge were about 98, 101, and 67%, respectively, with limits of detection of 0.04, 0.02, and 0.06 mg/L, respectively, which met the regulatory requirements. The present method was used for assay in biological monitoring of workers exposed to NMP in their occupational environment.

Chemical characterization of the acid alteration of diesel fuel: Non-targeted analysis by two-dimensional gas chromatography coupled with time-of-flight mass spectrometry with tile-based Fisher ratio and combinatorial threshold determination.

Science.gov (United States)

Parsons, Brendon A; Pinkerton, David K; Wright, Bob W; Synovec, Robert E

2016-04-01

The illicit chemical alteration of petroleum fuels is of keen interest, particularly to regulatory agencies that set fuel specifications, or taxes/credits based on those specifications. One type of alteration is the reaction of diesel fuel with concentrated sulfuric acid. Such reactions are known to subtly alter the chemical composition of the fuel, particularly the aromatic species native to the fuel. Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS) is well suited for the analysis of diesel fuel, but may provide the analyst with an overwhelming amount of data, particularly in sample-class comparison experiments comprised of many samples. Tile-based Fisher-ratio (F-ratio) analysis reduces the abundance of data in a GC×GC-TOFMS experiment to only the peaks which significantly distinguish the unaltered and acid altered sample classes. Three samples of diesel fuel from differently branded filling stations were each altered to discover chemical features, i.e., analyte peaks, which were consistently changed by the acid reaction. Using different fuels prioritizes the discovery of features likely to be robust to the variation present between fuel samples and may consequently be useful in determining whether an unknown sample has been acid altered. The subsequent analysis confirmed that aromatic species are removed by the acid alteration, with the degree of removal consistent with predicted reactivity toward electrophilic aromatic sulfonation. Additionally, we observed that alkenes and alkynes were also removed from the fuel, and that sulfur dioxide or compounds that degrade to sulfur dioxide are generated by the acid alteration. In addition to applying the previously reported tile-based F-ratio method, this report also expands null distribution analysis to algorithmically determine an F-ratio threshold to confidently select only the features which are sufficiently class-distinguishing. When applied to the acid

Supercritical fluid chromatography-A Hybrid of GC and LC

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Neha Sethi

2010-01-01

Full Text Available High performance specifications and unique functionality of chromatographic techniques is a demand of pharmaceutical industry and research. This leads to the origin of Supercritical Fluid Chromatography (SFC. It is a rapidly expanding analytical technique. The main feature that differentiates SFC from other chromatographic techniques is the replacement of either the liquid or gas mobile phase with a supercritical fluid mobile phase. It is considered a hybrid of GC and LC technique. High diffusion coefficient and low viscosity of supercritical fluids is responsible for high speed analysis, high efficiency and high sensitivity. Low mobile-phase flow rate, density programming and compatability with GC and LC detectors make SFC a versatile chromatographic technique in analytical re-search and development. It has a unique characteristic of analyzing thermo labile or non-volatile substances. This review highlights the role of supercritical fluid chromatography in the separation of polymers, thermally labile pesticides, fatty acids, metal chelates and organometallic compounds, chiral and achiral molecules, identification and analysis of polar samples, explosives, drugs of abuse and application of SFC in forensic science (fingerprint-ing.

Fully Automated Trimethylsilyl (TMS) Derivatisation Protocol for Metabolite Profiling by GC-MS.

Science.gov (United States)

Zarate, Erica; Boyle, Veronica; Rupprecht, Udo; Green, Saras; Villas-Boas, Silas G; Baker, Philip; Pinu, Farhana R

2016-12-29

Gas Chromatography-Mass Spectrometry (GC-MS) has long been used for metabolite profiling of a wide range of biological samples. Many derivatisation protocols are already available and among these, trimethylsilyl (TMS) derivatisation is one of the most widely used in metabolomics. However, most TMS methods rely on off-line derivatisation prior to GC-MS analysis. In the case of manual off-line TMS derivatisation, the derivative created is unstable, so reduction in recoveries occurs over time. Thus, derivatisation is carried out in small batches. Here, we present a fully automated TMS derivatisation protocol using robotic autosamplers and we also evaluate a commercial software, Maestro available from Gerstel GmbH. Because of automation, there was no waiting time of derivatised samples on the autosamplers, thus reducing degradation of unstable metabolites. Moreover, this method allowed us to overlap samples and improved throughputs. We compared data obtained from both manual and automated TMS methods performed on three different matrices, including standard mix, wine, and plasma samples. The automated TMS method showed better reproducibility and higher peak intensity for most of the identified metabolites than the manual derivatisation method. We also validated the automated method using 114 quality control plasma samples. Additionally, we showed that this online method was highly reproducible for most of the metabolites detected and identified (RSD TMS method has been applied to analyse a large number of complex plasma samples. Furthermore, we found that this method was highly applicable for routine metabolite profiling (both targeted and untargeted) in any metabolomics laboratory.

Effects of sample injection amount and time-of-flight mass spectrometric detection dynamic range on metabolome analysis by high-performance chemical isotope labeling LC-MS.

Science.gov (United States)

Zhou, Ruokun; Li, Liang

2015-04-06

The effect of sample injection amount on metabolome analysis in a chemical isotope labeling (CIL) liquid chromatography-mass spectrometry (LC-MS) platform was investigated. The performance of time-of-flight (TOF) mass spectrometers with and without a high-dynamic-range (HD) detection system was compared in the analysis of (12)C2/(13)C2-dansyl labeled human urine samples. An average of 1635 ± 21 (n = 3) peak pairs or putative metabolites was detected using the HD-TOF-MS, compared to 1429 ± 37 peak pairs from a conventional or non-HD TOF-MS. In both instruments, signal saturation was observed. However, in the HD-TOF-MS, signal saturation was mainly caused by the ionization process, while in the non-HD TOF-MS, it was caused by the detection process. To extend the MS detection range in the non-HD TOF-MS, an automated switching from using (12)C to (13)C-natural abundance peaks for peak ratio calculation when the (12)C peaks are saturated has been implemented in IsoMS, a software tool for processing CIL LC-MS data. This work illustrates that injecting an optimal sample amount is important to maximize the metabolome coverage while avoiding the sample carryover problem often associated with over-injection. A TOF mass spectrometer with an enhanced detection dynamic range can also significantly increase the number of peak pairs detected. In chemical isotope labeling (CIL) LC-MS, relative metabolite quantification is done by measuring the peak ratio of a (13)C2-/(12)C2-labeled peak pair for a given metabolite present in two comparative samples. The dynamic range of peak ratio measurement does not need to be very large, as only subtle changes of metabolite concentrations are encountered in most metabolomic studies where relative metabolome quantification of different groups of samples is performed. However, the absolute concentrations of different metabolites can be very different, requiring a technique to provide a wide detection dynamic range to allow the detection of as

Use of a Deuterated Internal Standard with Pyrolysis-GC/MS Dimeric Marker Analysis to Quantify Tire Tread Particles in the Environment

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Julie M. Panko

2012-11-01

Full Text Available Pyrolysis(pyr-GC/MS analysis of characteristic thermal decomposition fragments has been previously used for qualitative fingerprinting of organic sources in environmental samples. A quantitative pyr-GC/MS method based on characteristic tire polymer pyrolysis products was developed for tread particle quantification in environmental matrices including soil, sediment, and air. The feasibility of quantitative pyr-GC/MS analysis of tread was confirmed in a method evaluation study using artificial soil spiked with known amounts of cryogenically generated tread. Tread concentration determined by blinded analyses was highly correlated (r2 ³ 0.88 with the known tread spike concentration. Two critical refinements to the initial pyrolysis protocol were identified including use of an internal standard and quantification by the dimeric markers vinylcyclohexene and dipentene, which have good specificity for rubber polymer with no other appreciable environmental sources. A novel use of deuterated internal standards of similar polymeric structure was developed to correct the variable analyte recovery caused by sample size, matrix effects, and ion source variability. The resultant quantitative pyr-GC/MS protocol is reliable and transferable between laboratories.

Use of a deuterated internal standard with pyrolysis-GC/MS dimeric marker analysis to quantify tire tread particles in the environment.

Science.gov (United States)

Unice, Kenneth M; Kreider, Marisa L; Panko, Julie M

2012-11-08

Pyrolysis(pyr)-GC/MS analysis of characteristic thermal decomposition fragments has been previously used for qualitative fingerprinting of organic sources in environmental samples. A quantitative pyr-GC/MS method based on characteristic tire polymer pyrolysis products was developed for tread particle quantification in environmental matrices including soil, sediment, and air. The feasibility of quantitative pyr-GC/MS analysis of tread was confirmed in a method evaluation study using artificial soil spiked with known amounts of cryogenically generated tread. Tread concentration determined by blinded analyses was highly correlated (r2 ≥ 0.88) with the known tread spike concentration. Two critical refinements to the initial pyrolysis protocol were identified including use of an internal standard and quantification by the dimeric markers vinylcyclohexene and dipentene, which have good specificity for rubber polymer with no other appreciable environmental sources. A novel use of deuterated internal standards of similar polymeric structure was developed to correct the variable analyte recovery caused by sample size, matrix effects, and ion source variability. The resultant quantitative pyr-GC/MS protocol is reliable and transferable between laboratories.

An environmentally-friendly, highly efficient, gas pressure-assisted sample introduction system for ICP-MS and its application to detection of cadmium and lead in human plasma.

Science.gov (United States)

Cao, Yupin; Deng, Biyang; Yan, Lizhen; Huang, Hongli

2017-05-15

An environmentally friendly and highly efficient gas pressure-assisted sample introduction system (GPASIS) was developed for inductively-coupled plasma mass spectrometry. A GPASIS consisting of a gas-pressure control device, a customized nebulizer, and a custom-made spray chamber was fabricated. The advantages of this GPASIS derive from its high nebulization efficiencies, small sample volume requirements, low memory effects, good precision, and zero waste emission. A GPASIS can continuously, and stably, nebulize 10% NaCl solution for more than an hour without clogging. Sensitivity, detection limits, precision, long-term stability, double charge and oxide ion levels, nebulization efficiencies, and matrix effects of the sample introduction system were evaluated. Experimental results indicated that the performance of this GPASIS, was equivalent to, or better than, those obtained by conventional sample introduction systems. This GPASIS was successfully used to determine Cd and Pb by ICP-MS in human plasma. Copyright © 2017 Elsevier B.V. All rights reserved.

Monoterpene separation by coupling proton transfer reaction time-of-flight mass spectrometry with fastGC.

Science.gov (United States)

Materić, Dušan; Lanza, Matteo; Sulzer, Philipp; Herbig, Jens; Bruhn, Dan; Turner, Claire; Mason, Nigel; Gauci, Vincent

2015-10-01

Proton transfer reaction mass spectrometry (PTR-MS) is a well-established technique for real-time analysis of volatile organic compounds (VOCs). Although it is extremely sensitive (with sensitivities of up to 4500 cps/ppbv, limits of detection monoterpenes, which belong to the most important plant VOCs, still cannot be distinguished so more traditional technologies, such as gas chromatography mass spectrometry (GC-MS), have to be utilised. GC-MS is very time consuming (up to 1 h) and cannot be used for real-time analysis. Here, we introduce a sensitive, near-to-real-time method for plant monoterpene research-PTR-MS coupled with fastGC. We successfully separated and identified six of the most abundant monoterpenes in plant studies (α- and β-pinenes, limonene, 3-carene, camphene and myrcene) in less than 80 s, using both standards and conifer branch enclosures (Norway spruce, Scots pine and black pine). Five monoterpenes usually present in Norway spruce samples with a high abundance were separated even when the compound concentrations were diluted to 20 ppbv. Thus, fastGC-PTR-ToF-MS was shown to be an adequate one-instrument solution for plant monoterpene research.

Chemical Analysis of Essential oil of "Artemisia haussknechtii Boiss" by GC and GC/ MS

Directory of Open Access Journals (Sweden)

A. Nassir- Ahraadi . A. Rustaiyan

1994-08-01

Full Text Available The composition of the essential oil from the leaves and flowers of "Artemisia haussknechtii Boiss growing wild in the north-west of Iran, was investigated by GC and GC/MS."nThe main components of the volatile oil were 1,8 - cineol (16.5%, camphor (14.1%. artemisia ketone (10.5%, fragranol (9.0%, Yomogi alcohol (7.5% and B- pinene (5.4%. The total contribution of these compounds to the oil amounted to 63.0%."nMonoterpens and sesquiterpenes represent 90.08% and 1.52% of the oil respectively. Of the twenty oxygen-containing monoterpenes which made up a fairly large fraction of the terpenoid composition, the predominant components were 1,8 - cineole and camphor.

GC/MS-based profiling of amino acids and TCA cycle-related molecules in ulcerative colitis.

Science.gov (United States)

Ooi, Makoto; Nishiumi, Shin; Yoshie, Tomoo; Shiomi, Yuuki; Kohashi, Michitaka; Fukunaga, Ken; Nakamura, Shiro; Matsumoto, Takayuki; Hatano, Naoya; Shinohara, Masakazu; Irino, Yasuhiro; Takenawa, Tadaomi; Azuma, Takeshi; Yoshida, Masaru

2011-09-01

The roles that amino acids play in immunity and inflammation are well defined, and the relationship between inflammatory bowel disease (IBD) and certain amino acids has recently attracted attention. In this study, the levels of amino acids and trichloroacetic acid (TCA) cycle-related molecules in the colonic tissues and sera of patients with ulcerative colitis (UC) were profiled by gas chromatography/mass spectrometry (GC/MS), with the aim of evaluating whether the clinical state induced by UC leads to variations in the amino acid profile. Colonic biopsy samples from 22 UC patients were used, as well as serum samples from UC patients (n = 13), Crohn's disease (CD) patients (n = 21), and healthy volunteers (n = 17). In the GC/MS-based profiling of amino acids and TCA cycle-related molecules, lower levels of 16 amino acids and 5 TCA cycle-related molecules were observed in the colonic lesion tissues of the UC patients, and the serum profiles of amino acids and TCA cycle-related molecules of the UC patients were different from those of the CD patients and healthy volunteers. Our study raises the possibility that GC/MS-based profiling of amino acids and TCA cycle-related molecules is a useful early diagnostic tool for UC.

Determination of six phthalates in polypropylene consumer products by sonication-assisted extraction/ GC-MS methods

International Nuclear Information System (INIS)

Wei, Chong Kian; Fung, Loke Chui; Pang, Michelle

2011-01-01

Studies on determination of six kinds of phthalates, for example dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), benzyl butyl phthalate (BBP), di-(2-ethylhexyl) phthalate (DEHP), and di-n-octyl phthalate (DnOP), in three kinds of plastic containers for food use, including food container, instant noodle cup and snack container, by gas chromatography in combination with mass spectrometry detector (GC-MS) in electronic ionization mode with selected-ion monitoring (SIM) acquisition method (GC-MS(EI-SIM)) have been carried out. Extraction, clean-up and analysis methods have been developed and optimized. Determination of samples were performed after sonication-assisted extraction with 1:9 toluene and dichloromethane, clean-up with Bio-Beads S-X8 gel-permeation column and analyzed by GC-MS methods. The characteristic ions, 163, 194 for DMP; 149, 177, 222 for DEP; 149, 233, 251 for DBP; 91, 149, 206 for BBP; 149, 176, 193 for DEHP; 149, 167, 279 for DNOP were chosen for quantitative studies. These techniques are possible to detect phthalates at the level of 1-70 mg/ kg. The overall recoveries were 79.2-91.1 % with relative standard deviation (R.S.D.) values at 3.1-11.3 %. Only DEHP was detected in the studied samples. (author)

Different methods for volatile sampling in mammals.

Directory of Open Access Journals (Sweden)

Marlen Kücklich

Full Text Available Previous studies showed that olfactory cues are important for mammalian communication. However, many specific compounds that convey information between conspecifics are still unknown. To understand mechanisms and functions of olfactory cues, olfactory signals such as volatile compounds emitted from individuals need to be assessed. Sampling of animals with and without scent glands was typically conducted using cotton swabs rubbed over the skin or fur and analysed by gas chromatography-mass spectrometry (GC-MS. However, this method has various drawbacks, including a high level of contaminations. Thus, we adapted two methods of volatile sampling from other research fields and compared them to sampling with cotton swabs. To do so we assessed the body odor of common marmosets (Callithrix jacchus using cotton swabs, thermal desorption (TD tubes and, alternatively, a mobile GC-MS device containing a thermal desorption trap. Overall, TD tubes comprised most compounds (N = 113, with half of those compounds being volatile (N = 52. The mobile GC-MS captured the fewest compounds (N = 35, of which all were volatile. Cotton swabs contained an intermediate number of compounds (N = 55, but very few volatiles (N = 10. Almost all compounds found with the mobile GC-MS were also captured with TD tubes (94%. Hence, we recommend TD tubes for state of the art sampling of body odor of mammals or other vertebrates, particularly for field studies, as they can be easily transported, stored and analysed with high performance instruments in the lab. Nevertheless, cotton swabs capture compounds which still may contribute to the body odor, e.g. after bacterial fermentation, while profiles from mobile GC-MS include only the most abundant volatiles of the body odor.

Use of capillary GC-MS for identification of radiation-induced DNA base damage: Implications for base-excision repair of DNA

International Nuclear Information System (INIS)

Dizdaroglu, M.

1985-01-01

Application of GC-MS to characterization of radiation-induced base products of DNA and DNa base-amino acid crosslinks is presented. Samples of γ-irradiated DNa were hydrolyzed with formic acid, trimethylsilylated and subjected to GC-MS analysis using a fused silica capillary column. Hydrolysis conditions suitable for the simultaneous analysis of the radiation-induced products of all four DNA bases in a single run were determined. The trimethylsilyl derivatives of these products had excellent GC-properties and easily interpretable mass spectra. The complementary use of t-butyldimetylsilyl derivatives was also demonstrated. Moreover, the usefulness of this method for identification of radiation-induced DNA base-amino acid crosslinks was shown using γ-irradiated mixtures of thymine and tyrosine or phenylalanine. Because of the excellent resolving power of capillary GC and the instant and highly sensitive identification by MS, GC-MS is suggested as a suitable technique for identification of altered bases removed from DNA by base-excision repair enzymes

Atypical excretion profile and GC/C/IRMS findings may last for nine months after a single dose of nandrolone decanoate.

Science.gov (United States)

Palonek, Elzbieta; Ericsson, Magnus; Gårevik, Nina; Rane, Anders; Lehtihet, Mikael; Ekström, Lena

2016-04-01

The use of the anabolic androgenic steroid nandrolone and its prohormones is prohibited in sport. A common route of nandrolone administration is intramuscular injections of a nandrolone ester. Here we have investigated the detection time of nandrolone and 19-norandrosterone and 19-noretiocholanolone metabolites in eleven healthy men after the administration of a 150 mg dose of nandrolone decanoate. The urinary concentrations of nandrolone and the metabolites were monitored by GC-MS/MS for nine months and in some samples the presence of 19-norandrosterone was confirmed by GC/C/IRMS analysis. The participants were genotyped for polymorphisms in PDE7B1 and UGT2B15 genes previously shown to influence the activation and inactivation of nandrolone decanoate. There were large inter-individual variations in the excretion rate of nandrolone and the metabolites, although not related to genetic variations in the UGT2B15 (rs1902023) and PDE7B1 (rs7774640) genes. After the administration, 19-norandrosterone was found at 2-8-fold higher concentrations than 19-noretiocholanolone. We showed that nandrolone doping can be identified 4 and 9 months after the injection of only one single dose in six and three individuals, respectively. We also noted that GC/C/IRMS confirms the presence of exogenous 19-norandrosterone in the urine samples, showing δ13 values around -32 ‰. This was true even in a sample that was not identified as an atypical finding after the GC-MS/MS analysis further showing the power of using GC/C/IRMS in routine anti-doping settings. Copyright © 2016 Elsevier Inc. All rights reserved.

32-Week Holding-Time Study of SUMMA Polished Canisters and Triple Sorbent Traps Used To Sample Organic Constituents in Radioactive Waste Tank Vapor Headspace

International Nuclear Information System (INIS)

Evans, John C.; Huckaby, James L.; Mitroshkov, Alexandre V.; Julya, Janet L.; Hayes, James C.; Edwards, Jeffrey A.; Sasaki, Leela M.

1997-01-01

Two sampling methods[SUMMA polished canisters and triple sorbent traps (TSTs)] were compared for long-term storage of trace organic vapor samples collected from the headspaces of high-level radioactive waste tanks at the U.S. Department of Energy's Hanford Site in Washington State. Because safety, quality assurance, radiological controls, the long-term stability of the sampling media during storage needed to be addressed. Samples were analyzed with a gas chromatograph/mass spectrometer (GC/MS) using cryogenic reconcentration or thermal desorption sample introduction techniques. SUMMA canister samples were also analyzed for total non-methane organic compounds (TNMOC) by GC/flame ionization detector (FID) using EPA Compendium Method TO-12 . To verify the long-term stability of the sampling media, multiple samples were collected in parallel from a typical passively ventilated radioactive waste tank known to contain moderately high concentrations of both polar and nonpolar organic compounds. Analyses for organic analytes and TNMOC were conducted at increasing intervals over a 32-week period to determine whether any systematic degradation of sample integrity occurred. Analytes collected in the SUMMA polished canisters generally showed good stability over the full 32 weeks with recoveries at the 80% level or better for all compounds studied. The TST data showed some loss (50-80% recovery) for a few high-volatility compounds even in the refrigerated samples; losses for unrefrigerated samples were far more pronounced with recoveries as low as 20% observed in a few cases

Evaluation of analytical performance and reliability of direct nanoLC-nanoESI-high resolution mass spectrometry for profiling the (xeno)metabolome.

Science.gov (United States)

Chetwynd, Andrew J; David, Arthur; Hill, Elizabeth M; Abdul-Sada, Alaa

2014-10-01

Mass spectrometry (MS) profiling techniques are used for analysing metabolites and xenobiotics in biofluids; however, detection of low abundance compounds using conventional MS techniques is poor. To counter this, nanoflow ultra-high-pressure liquid chromatography-nanoelectrospray ionization-time-of-flight MS (nUHPLC-nESI-TOFMS), which has been used primarily for proteomics, offers an innovative prospect for profiling small molecules. Compared to conventional UHPLC-ESI-TOFMS, nUHPLC-nESI-TOFMS enhanced detection limits of a variety of (xeno)metabolites by between 2 and 2000-fold. In addition, this study demonstrates for the first time excellent repeatability and reproducibility for analysis of urine and plasma samples using nUHPLC-nESI-TOFMS, supporting implementation of this platform as a novel approach for high-throughput (xeno)metabolomics. Copyright © 2014 John Wiley & Sons, Ltd.

Bromination of Aromatic Compounds by Residual Bromide in Sodium Chloride Matrix Modifier Salt During Heated Headspace GC/MS Analysis

Science.gov (United States)

Analytical artifacts attributed to the bromination of toluene, xylenes, and trimethylbenzenes were found during the heated headspace gas chromatography/mass spectrometry (GC/MS) analysis of aqueous samples. The aqueous samples were produced from Fenton-like chemical oxidation rea...

Effect of Genetics, Environment, and Phenotype on the Metabolome of Maize Hybrids Using GC/MS and LC/MS.

Science.gov (United States)

Tang, Weijuan; Hazebroek, Jan; Zhong, Cathy; Harp, Teresa; Vlahakis, Chris; Baumhover, Brian; Asiago, Vincent

2017-06-28

We evaluated the variability of metabolites in various maize hybrids due to the effect of environment, genotype, phenotype as well as the interaction of the first two factors. We analyzed 480 forage and the same number of grain samples from 21 genetically diverse non-GM Pioneer brand maize hybrids, including some with drought tolerance and viral resistance phenotypes, grown at eight North American locations. As complementary platforms, both GC/MS and LC/MS were utilized to detect a wide diversity of metabolites. GC/MS revealed 166 and 137 metabolites in forage and grain samples, respectively, while LC/MS captured 1341 and 635 metabolites in forage and grain samples, respectively. Univariate and multivariate analyses were utilized to investigate the response of the maize metabolome to the environment, genotype, phenotype, and their interaction. Based on combined percentages from GC/MS and LC/MS datasets, the environment affected 36% to 84% of forage metabolites, while less than 7% were affected by genotype. The environment affected 12% to 90% of grain metabolites, whereas less than 27% were affected by genotype. Less than 10% and 11% of the metabolites were affected by phenotype in forage and grain, respectively. Unsupervised PCA and HCA analyses revealed similar trends, i.e., environmental effect was much stronger than genotype or phenotype effects. On the basis of comparisons of disease tolerant and disease susceptible hybrids, neither forage nor grain samples originating from different locations showed obvious phenotype effects. Our findings demonstrate that the combination of GC/MS and LC/MS based metabolite profiling followed by broad statistical analysis is an effective approach to identify the relative impact of environmental, genetic and phenotypic effects on the forage and grain composition of maize hybrids.

[Recent advances in analysis of petroleum geological samples by comprehensive two-dimensional gas chromatography].

Science.gov (United States)

Gao, Xuanbo; Chang, Zhenyang; Dai, Wei; Tong, Ting; Zhang, Wanfeng; He, Sheng; Zhu, Shukui

2014-10-01

Abundant geochemical information can be acquired by analyzing the chemical compositions of petroleum geological samples. The information obtained from the analysis provides scientifical evidences for petroleum exploration. However, these samples are complicated and can be easily influenced by physical (e. g. evaporation, emulsification, natural dispersion, dissolution and sorption), chemical (photodegradation) and biological (mainly microbial degradation) weathering processes. Therefore, it is very difficult to analyze the petroleum geological samples and they cannot be effectively separated by traditional gas chromatography/mass spectrometry. A newly developed separation technique, comprehensive two-dimensional gas chromatography (GC x GC), has unique advantages in complex sample analysis, and recently it has been applied to petroleum geological samples. This article mainly reviews the research progres- ses in the last five years, the main problems and the future research about GC x GC applied in the area of petroleum geology.

In situ loading of Ag_2WO_4 on ultrathin g-C_3N_4 nanosheets with highly enhanced photocatalytic performance

International Nuclear Information System (INIS)

Li, Yunfeng; Jin, Renxi; Fang, Xu; Yang, Yang; Yang, Man; Liu, Xianchun; Xing, Yan; Song, Shuyan

2016-01-01

Graphical abstract: Ultrathin g-C_3N_4 nanosheets (g-C_3N_4−NS) with improved electron transport ability and large number of active sites are employed instead of bulk g-C_3N_4 to prepare the Ag_2WO_4/g-C_3N_4−NS heterostructured photocatalysts, which exhibit remarkable photocatalytic activity for wastewater treatment. - Highlights: • Ag2WO4/g-C3N4-NS photocatalysts were obtained by a deposition-precipitation method. • Ag2WO4/g-C3N4-NS possess large surface areas and increased lifetime of charges. • Ag2WO4/g-C3N4-NS exhibit enhanced activity on degradation of RhB and MO. • The photocatalytic mechanism of the Ag2WO4/g-C3N4-NS system were investigated. - Abstract: The g-C_3N_4 nanosheets (g-C_3N_4−NS) exhibit more excellent property than common bulk g-C_3N_4 (g-C_3N_4-B) due to their large surface areas, improved electron transport ability and well dispersion in water. In this work, ultrathin g-C_3N_4−NS with a thickness of about 2.7 nm have been synthesized by a simple thermal exfoliation of bulk g-C_3N_4, and then Ag_2WO_4 nanoparticles are in situ loaded on their surface to construct the Ag_2WO_4/g-C_3N_4−NS heterostructured photocatalysts. Due to their unique physicochemical properties, the as-prepared heterostructures possess a fast interfacial charge transfer and increased lifetime of photo-excited charge carriers, and exhibit much higher photocatalytic activity. Under visible light irradiation, the optimum photocatalytic activity of Ag_2WO_4/g-C_3N_4−NS composites is almost 53.6 and 26.5 times higher than that of pure g-C_3N_4-B and Ag_2WO_4/g-C_3N_4-B heterostructures towards the degradation of rhodamine B, respectively, and is almost 30.6 and 9.8 times higher towards the degradation of methyl orange, respectively. In addition, the natural sunlight photocatalytic activities of the as-prepared samples are also investigated.

Gas-phase sample introduction techniques for the determination of some non-metals by ICP-AES, MIP-AES AND ICP-MS

International Nuclear Information System (INIS)

Nakahara, Taketoshi

2003-01-01

Various gas-phase sample introduction methods in analytical atomic spectrometry have been documented for up to 30 elements, but only a few of these methods with less than one-third of the analytes exhibit adequate, competitive performance characteristics. Most attractive are the chemical systems based on (i) reactions in aqueous media, (ii) with fast kinetics of chemical vapor generation and easy stripping off of vapors from solution, (iii) reliable interference control, (iv) with high and reducible chemical yields of volatile products which are (v) readily atomized, excited or ionized in a plasma, so as to provide adequate sensitivity and low limits of detection (LOD). Some significant advantage of gas-phase sample introduction over the widely-used pneumatic nebulization of liquid (solution) samples are (1) high chemical yields and transport efficiency, (2) separation from troublesome matrices, (3) enrichment, (4) automation in flow injection and continuous flow mode, (5) good sample throughput rates, (6) competitive LODs and RSDs, (7) commercially available accessories, (8) economically affordable and (9) speciation potentialities. To the contrary, the major disadvantages and limitations are (1) complex, on line-chemistry involved, (2) specific sample pre-treatment required, (3) effect of oxidation and binding state of analyte, (4) chemical interferences, (5) foaming and aerosol formation, (6) numerous instrumental and chemical parameters for optimization, (7) applicability to a limited number of analytes, (8) limited linear ranges and (9) poor-multi-element capabilities.

Case Report: GcMAF Treatment in a Patient with Multiple Sclerosis.

Science.gov (United States)

Inui, Toshio; Katsuura, Goro; Kubo, Kentaro; Kuchiike, Daisuke; Chenery, Leslye; Uto, Yoshihiro; Nishikata, Takahito; Mette, Martin

2016-07-01

Gc protein-derived macrophage-activating factor (GcMAF) has various functions as an immune modulator, such as macrophage activation, anti-angiogenic activity and anti-tumor activity. Clinical trials of second-generation GcMAF demonstrated remarkable clinical effects in several types of cancers. Thus, GcMAF-based immunotherapy has a wide application for use in the treatment of many diseases via macrophage activation that can be used as a supportive therapy. Multiple sclerosis (MS) is considered to be an autoimmune disorder that affects the myelinated axons in the central nervous system (CNS). This study was undertaken to examine the effects of second-generation GcMAF in a patient with MS. This case study demonstrated that treatments of GcMAF in a patient with MS have potent therapeutic actions with early beneficial responses, especially improvement of motor dysfunction. GcMAF shows therapeutic potency in the treatment of MS. Copyright© 2016 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

Determination of phenobarbital in hair matrix by liquid phase microextraction (LPME) and gas chromatography-mass spectrometry (GC-MS).

Science.gov (United States)

Roveri, Flávia Lopes; Paranhos, Beatriz Aparecida Passos Bismara; Yonamine, Mauricio

2016-08-01

A method for identification and quantification of phenobarbital in hair samples by liquid phase microextraction (LPME) and gas chromatography-mass spectrometry (GC-MS) has been presented. Drug-free hair specimens were collected and separated in 50mg aliquots. Each aliquot was washed with 2.0mL of dichloromethane for 15min at 37°C. Standards and deuterated internal standards for calibration and quality control samples were added to the washed hair aliquot and the sample was submitted to complete digestion with sodium hydroxide (NaOH) 1.0mol/L for 15min at 70°C. The dissolved sample was submitted to LPME. After extraction, the residue was derivatized with tetramethylammonium hydroxide (TMAH) and analyzed by GC-MS. The limit of detection (LOD) was 0.1ng/mg and the limit of quantification (LOQ) was 0.25ng/mg. The calibration curve was linear over a concentration range of 0.25ng/mg to 10ng/mg (r(2)>0.99). The intra- and inter-assay precisions, given by RSD, were less than 6% for phenobarbital. Fortified samples of secobarbital and pentobarbital were also submitted to the validated method. The method was successfully applied to hair samples collected from three volunteers who reported regular use of phenobarbital (clinical treatment). The concentrations found were 9.5, 15.1 and 16.3ng/mg of phenobarbital. To contemplate the concentrations found, dilution integrity tests were also validated. The LPME and GC-MS method showed to be suitable for the detection of phenobarbital in hair samples and can be promptly used for different purposes whenever required. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

PY-GC-MS applied to the identification of synthetic resins in Brazilian painting

International Nuclear Information System (INIS)

Redigolo, Marcelo M.; Amaral, Priscila O.; Leao, Claudio; Crepaldi, Caike; Munita, Casimiro S.; Bustillos, Oscar V.; Russo, Tatiana; Mendonca, Valeria de

2015-01-01

Works of art are appreciated for their material and immaterial value. Restoring objects of art is a delicate procedure, mostly due to the irreversibility of the interventions. Hence, it is recommended to study the chemical composition of the object to avoid errors. The premise for restoring or conserving these objects is their physical preservation, i.e., it is advisable to avoid sampling and, when necessary, samples must be minute. The analytical techniques that fulfill these requirements are limited. Mass spectrometry (MS) is a versatile technique due to its hyphenation possibilities. Recently, it has being employed in the identification of natural and synthetic resins in works of art. Electron ionization (EI) is a powerful method of molecular fragmentation employed in the detection of volatile organic compounds by mass spectrometry. In this work, two micrograms (μg) of sample from a Brazilian contemporary painting were analyzed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) technique. A microfurnace-type pyrolyzer was coupled to a gas chromatograph, using a non-polar capillary column. The electron ionization was achieved applying 70 eV electron energy. This technique is suitable for the analysis of material from objects of art, being specific, accurate and requiring minimal sampling. The synthetic resin diallyl phthalate (DAP) was identified by the Py-GC/MS technique. (author)

PY-GC-MS applied to the identification of synthetic resins in Brazilian painting

Energy Technology Data Exchange (ETDEWEB)

Redigolo, Marcelo M.; Amaral, Priscila O.; Leao, Claudio; Crepaldi, Caike; Munita, Casimiro S.; Bustillos, Oscar V., E-mail: marcelo.redigolo@usp.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Russo, Tatiana; Mendonca, Valeria de [Pinacoteca do Estado de Sao Paulo, SP (Brazil)

2015-07-01

Works of art are appreciated for their material and immaterial value. Restoring objects of art is a delicate procedure, mostly due to the irreversibility of the interventions. Hence, it is recommended to study the chemical composition of the object to avoid errors. The premise for restoring or conserving these objects is their physical preservation, i.e., it is advisable to avoid sampling and, when necessary, samples must be minute. The analytical techniques that fulfill these requirements are limited. Mass spectrometry (MS) is a versatile technique due to its hyphenation possibilities. Recently, it has being employed in the identification of natural and synthetic resins in works of art. Electron ionization (EI) is a powerful method of molecular fragmentation employed in the detection of volatile organic compounds by mass spectrometry. In this work, two micrograms (μg) of sample from a Brazilian contemporary painting were analyzed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) technique. A microfurnace-type pyrolyzer was coupled to a gas chromatograph, using a non-polar capillary column. The electron ionization was achieved applying 70 eV electron energy. This technique is suitable for the analysis of material from objects of art, being specific, accurate and requiring minimal sampling. The synthetic resin diallyl phthalate (DAP) was identified by the Py-GC/MS technique. (author)

G+C content dominates intrinsic nucleosome occupancy

Directory of Open Access Journals (Sweden)

Hughes Timothy R

2009-12-01

Full Text Available Abstract Background The relative preference of nucleosomes to form on individual DNA sequences plays a major role in genome packaging. A wide variety of DNA sequence features are believed to influence nucleosome formation, including periodic dinucleotide signals, poly-A stretches and other short motifs, and sequence properties that influence DNA structure, including base content. It was recently shown by Kaplan et al. that a probabilistic model using composition of all 5-mers within a nucleosome-sized tiling window accurately predicts intrinsic nucleosome occupancy across an entire genome in vitro. However, the model is complicated, and it is not clear which specific DNA sequence properties are most important for intrinsic nucleosome-forming preferences. Results We find that a simple linear combination of only 14 simple DNA sequence attributes (G+C content, two transformations of dinucleotide composition, and the frequency of eleven 4-bp sequences explains nucleosome occupancy in vitro and in vivo in a manner comparable to the Kaplan model. G+C content and frequency of AAAA are the most important features. G+C content is dominant, alone explaining ~50% of the variation in nucleosome occupancy in vitro. Conclusions Our findings provide a dramatically simplified means to predict and understand intrinsic nucleosome occupancy. G+C content may dominate because it both reduces frequency of poly-A-like stretches and correlates with many other DNA structural characteristics. Since G+C content is enriched or depleted at many types of features in diverse eukaryotic genomes, our results suggest that variation in nucleotide composition may have a widespread and direct influence on chromatin structure.

A review on g-C3N4-based photocatalysts

International Nuclear Information System (INIS)

Wen, Jiuqing; Xie, Jun; Chen, Xiaobo; Li, Xin

2017-01-01

Graphical abstract: The photocatalytic fundamentals, versatile properties, design strategies and potential applications of g-C 3 N 4 -based photocatalysts were systematically summarized and addressed. - Highlights: • The photocatalytic fundamentals of g-C 3 N 4 were systematically summarized. • The versatile properties of g-C 3 N 4 photocatalysts were highlighted. • The different design strategies of g-C 3 N 4 photocatalysts were reviewed. • The important photocatalytic applications of g-C 3 N 4 were also addressed. - Abstract: As one of the most appealing and attractive technologies, heterogeneous photocatalysis has been utilized to directly harvest, convert and store renewable solar energy for producing sustainable and green solar fuels and a broad range of environmental applications. Due to their unique physicochemical, optical and electrical properties, a wide variety of g-C 3 N 4 -based photocatalysts have been designed to drive various reduction and oxidation reactions under light irradiation with suitable wavelengths. In this review, we have systematically summarized the photocatalytic fundamentals of g-C 3 N 4 -based photocatalysts, including fundamental mechanism of heterogeneous photocatalysis, advantages, challenges and the design considerations of g-C 3 N 4 -based photocatalysts. The versatile properties of g-C 3 N 4 -based photocatalysts are highlighted, including their crystal structural, surface phisicochemical, stability, optical, adsorption, electrochemical, photoelectrochemical and electronic properties. Various design strategies are also thoroughly reviewed, including band-gap engineering, defect control, dimensionality tuning, pore texture tailoring, surface sensitization, heterojunction construction, co-catalyst and nanocarbon loading. Many important applications are also addressed, such as photocatalytic water splitting (H 2 evolution and overall water splitting), degradation of pollutants, carbon dioxide reduction, selective organic

Bacteriophage GC1, a Novel Tectivirus Infecting Gluconobacter Cerinus, an Acetic Acid Bacterium Associated with Wine-Making

Directory of Open Access Journals (Sweden)

Cécile Philippe

2018-01-01

Full Text Available The Gluconobacter phage GC1 is a novel member of the Tectiviridae family isolated from a juice sample collected during dry white wine making. The bacteriophage infects Gluconobacter cerinus, an acetic acid bacterium which represents a spoilage microorganism during wine making, mainly because it is able to produce ethyl alcohol and transform it into acetic acid. Transmission electron microscopy revealed tail-less icosahedral particles with a diameter of ~78 nm. The linear double-stranded DNA genome of GC1 (16,523 base pairs contains terminal inverted repeats and carries 36 open reading frames, only a handful of which could be functionally annotated. These encode for the key proteins involved in DNA replication (protein-primed family B DNA polymerase as well as in virion structure and assembly (major capsid protein, genome packaging ATPase (adenosine triphosphatase and several minor capsid proteins. GC1 is the first tectivirus infecting an alphaproteobacterial host and is thus far the only temperate tectivirus of gram-negative bacteria. Based on distinctive sequence and life-style features, we propose that GC1 represents a new genus within the Tectiviridae, which we tentatively named “Gammatectivirus”. Furthermore, GC1 helps to bridge the gap in the sequence space between alphatectiviruses and betatectiviruses.

Primary investigation on contamination pattern of legacy and emerging halogenated organic pollutions in freshwater fish from Liaohe River, Northeast China

Energy Technology Data Exchange (ETDEWEB)

Ren Guofa, E-mail: rgf2008@shu.edu.cn [Institute of Environmental Pollution and Health, School of Environment and Chemical Engineering, Shanghai University, 99 Shangda Road, Baoshan Disrict, Shanghai 200072 (China); Zhao, Wang [Institute of Environmental Pollution and Health, School of Environment and Chemical Engineering, Shanghai University, 99 Shangda Road, Baoshan Disrict, Shanghai 200072 (China); Zhiqiang, Yu [State Key Laboratory of Organic Geochemistry, Guangzhou Key Laboratory of Environment Protection and Resource Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Yang, Wang [Institute of Environmental Pollution and Health, School of Environment and Chemical Engineering, Shanghai University, 99 Shangda Road, Baoshan Disrict, Shanghai 200072 (China); Shengtao, Ma [State Key Laboratory of Organic Geochemistry, Guangzhou Key Laboratory of Environment Protection and Resource Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Minghong, Wu [Institute of Environmental Pollution and Health, School of Environment and Chemical Engineering, Shanghai University, 99 Shangda Road, Baoshan Disrict, Shanghai 200072 (China); Guoying, Sheng [State Key Laboratory of Organic Geochemistry, Guangzhou Key Laboratory of Environment Protection and Resource Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Jiamo, Fu [Institute of Environmental Pollution and Health, School of Environment and Chemical Engineering, Shanghai University, 99 Shangda Road, Baoshan Disrict, Shanghai 200072 (China); State Key Laboratory of Organic Geochemistry, Guangzhou Key Laboratory of Environment Protection and Resource Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)

2013-01-15

Legacy halogenated compounds, including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and emerging organo-halogen pollutants such as Dechlorane Plus (DP), were detected in fish from an old industrial region in Northeast China. PCBs and PBDEs were detected in all of the samples, with concentrations ranging from 38.15 to 170.51 ng/g lipid weight, and 9.40-39.69 ng/g lipid weight, respectively. DP was detected in more than 90% of the samples with concentrations ranging from not detected (ND) to 470 pg g/g lipid weight. Compared with similar data in other areas of the world, PCBs, PBDEs and DP in fish from Liaohe River were at medium or low level. An unusually high percentage of PCB-209 was first reported in the fish samples collected from China. Other halogenated pollutions, such as dichlorodiphenyltrichloroethane (DDT) and its metabolites, octachlorostyrene, chlorinated anisole, chlorinated thioanisole, triclosan-methyl, and other pesticides, have also been identified in the fish samples. - Highlights: Black-Right-Pointing-Pointer DP was reported in fish samples from river close to an old industrial base in China. Black-Right-Pointing-Pointer The first report on the unusually high fraction of PCB-209 in samples from China. Black-Right-Pointing-Pointer GC Multiplication-Sign GC-TOFMS was used to identify non-targeted halogenated pollutants. - An unusually high percentage of PCB-209 was first reported in the fish samples collected from China, which might indicate that there were distinct sources of pure PCB-209 in the region of Liaohe River.

On-line Automated Sample Preparation-Capillary Gas Chromatography for the Analysis of Plasma Samples.

NARCIS (Netherlands)

Louter, A.J.H.; van der Wagt, R.A.C.A.; Brinkman, U.A.T.

1995-01-01

An automated sample preparation module, (the automated sample preparation with extraction columns, ASPEC), was interfaced with a capillary gas chromatograph (GC) by means of an on-column interface. The system was optimised for the determination of the antidepressant trazodone in plasma. The clean-up

Simultaneous determination of organophosphorus pesticides and phthalates in baby food samples by ultrasound-vortex-assisted liquid-liquid microextraction and GC-IT/MS.

Science.gov (United States)

Notardonato, Ivan; Salimei, Elisabetta; Russo, Mario Vincenzo; Avino, Pasquale

2018-05-01

Baby foods are either a soft, liquid paste or an easily chewed food since babies lack developed muscles and teeth to chew effectively. Babies typically move to consuming baby food once nursing or formula is not sufficient for the child's appetite. Some commercial baby foods have been criticized for their contents. This article focuses on the simultaneous determination of organophosphorus pesticides and phthalates by means of a method based on ultrasound-vortex-assisted liquid-liquid microextraction coupled with gas chromatography-ion trap mass spectrometry (GC-IT/MS). The protocol developed allowed the determination of six phthalates [dimethyl phthalate, diethyl phthalate, dibutyl phthalate, isobutyl cyclohexyl phthalate, benzyl butyl phthalate, bis(2-ethylhexyl) phthalate] and 19 organophosphorus pesticides. Freeze-dried product samples (0.1-0.2 g) were dissolved in 10 mL of warm distilled water along with 5 μL of an internal standard (anthracene at 10 mg mL -1 in acetone): the choice of extraction solvent was studied, with the most suitable being n-heptane, which is used for phthalate determination in similar matrices. The solution, held for 5 min in a vortex mixer and for 6 min in a 100-W ultrasonic bath to favor solvent dispersion and consequently analyte extraction, was centrifuged at 4000 rpm for 30 min. Then 1 μL was injected into the GC-IT/MS system (SE-54 capillary column; length 30 m, inner diameter 250 μm, film thickness 0.25 μm). All analytical parameters investigated are discussed in depth. The method was applied to real commercial freeze-dried samples: significant contaminant concentrations were not found. Graphical abstract Simultaneous and sensitive determination of organophosphorus pesticides and phthalates in baby foods by the ultrasound-vortex-assisted liquid-liquid microextraction ֪gas chromatography-ion trap mass spectrometry procedure. 1 methacrifos, 2 pirofos, 3 phorate, 4 seraphos, 5 diazinon, 6 etrimphos, 7 dichlofenthion, 8

Changes in the molecular composition of crude oils during their preparation for GC and GC-MS analyses

Energy Technology Data Exchange (ETDEWEB)

Ahmed, M.; George, S.C. [CSIRO Petroleum, North Ryde, NSW (Australia)

2004-02-01

Rotary evaporation and nitrogen blowing are the two frequently used procedures in organic geochemistry laboratories to prepare crude oils and extractable organic matter for gas chromatography (GC) and GC-mass spectrometry (GC-MS) analyses. In this work, the effects of these preparatory procedures on the molecular composition have been comprehensively assessed for the first time, by evaporating 34 aliquots of North Sea Oil-1 dissolved in dichloromethane under a variety of conditions: (a) rotary evaporation with a reduced pressure of 80 to 60 kpa, and water bath temperatures of 30-60 {sup o}C, (b) nitrogen blowing, with flow rates of 130 to >850 ml/min and heater block temperatures of 30-60 {sup o}C, and (c) open vial evaporation in a refrigerator at 3 {sup o}C and in a fume cupboard at 22 {sup o}C. Analyses of the unaltered original oil, solution and the evaporated oil aliquots for 215 target compounds, from benzene to n-C{sub 32}, indicate that (1)sample is blown to dryness, higher nitrogen flow rates also cause more loss. The extent of compound loss generally increases with decreasing boiling points and molecular weights. However, some compounds such as C{sub 0}-C{sub 2} alkylbenzenes do not follow this trend and are particularly resistant to laboratory evaporation processes. Nitrogen blowing evaporation to dryness can results in substantial losses of

An evaluation of inductively coupled plasma optical emission spectrometry using electrothermal atomisation sample introduction and photographic plate detection

International Nuclear Information System (INIS)

Khathing, D.T.; Pickford, C.J.

1984-05-01

A photographic radiation measurement approach has been used with an inductively coupled plasma source to evaluate and tabulate the more prominent optical emission lines of 66 elements. Compared with the more common sample introduction technique using nebulisation, increased sensitivity for multielement analysis of small samples was achieved by using a simple graphite electrothermal atomisation system. This was constructed to serve as a dual purpose atomiser ie both for Atomic Absorption and for Inductively Coupled Plasma Emission spectroscopy. The system offers the advantage of a wide multi-elemental coverage, but sensitivities achieved with photographic detection are poorer than those obtained photoelectrically. (author)

Shock tube/time-of-flight mass spectrometer for high temperature kinetic studies

International Nuclear Information System (INIS)

Tranter, Robert S.; Giri, Binod R.; Kiefer, John H.

2007-01-01

A shock tube (ST) with online, time-of-flight mass spectrometric (TOF-MS) detection has been constructed for the study of elementary reactions at high temperature. The ST and TOF-MS are coupled by a differentially pumped molecular beam sampling interface, which ensures that the samples entering the TOF-MS are not contaminated by gases drawn from the cold end wall thermal boundary layer in the ST. Additionally, the interface allows a large range of postshock pressures to be used in the shock tube while maintaining high vacuum in the TOF-MS. The apparatus and the details of the sampling system are described along with an analysis in which cooling of the sampled gases and minimization of thermal boundary layer effects are discussed. The accuracy of kinetic measurements made with the apparatus has been tested by investigating the thermal unimolecular dissociation of cyclohexene to ethylene and 1,3-butadiene, a well characterized reaction for which considerable literature data that are in good agreement exist. The experiments were performed at nominal reflected shock wave pressures of 600 and 1300 Torr, and temperatures ranging from 1260 to 1430 K. The rate coefficients obtained are compared with the earlier shock tube studies and are found to be in very good agreement. As expected no significant difference is observed in the rate constant between pressures of 600 and 1300 Torr

GC Analyses of Salvia Seeds as Valuable Essential Oil Source

Directory of Open Access Journals (Sweden)

Mouna Ben Taârit

2014-01-01

Full Text Available The essential oils of seeds of Salvia verbenaca, Salvia officinalis, and Salvia sclarea were obtained by hydrodistillation and analyzed by gas chromatography (GC and GC-mass spectrometry. The oil yields (w/w were 0.050, 0.047, and 0.045% in S. verbenaca, S. sclarea, and S. officinalis, respectively. Seventy-five compounds were identified. The essential oil composition of S. verbenaca seeds showed that over 57% of the detected compounds were oxygenated monoterpenes followed by sesquiterpenes (24.04% and labdane type diterpenes (5.61%. The main essential oil constituents were camphor (38.94%, caryophyllene oxide (7.28%, and 13-epi-manool (5.61%, while those of essential oil of S. officinalis were α-thujone (14.77%, camphor (13.08%, and 1,8-cineole (6.66%. In samples of S. sclarea, essential oil consists mainly of linalool (24.25%, α-thujene (7.48%, linalyl acetate (6.90%, germacrene-D (5.88%, bicyclogermacrene (4.29%, and α-copaene (4.08%. This variability leads to a large range of naturally occurring volatile compounds with valuable industrial and pharmaceutical outlets.

First detection of an NSAID, flunixin, in sheep's wool using GC-MS

Energy Technology Data Exchange (ETDEWEB)

Richards, Ngaio, E-mail: ngaio.richards@anglia.ac.uk [Life Sciences, Anglia Ruskin University, East Road, Cambridge, CB1 1PT (United Kingdom); Hall, Sarah [Life Sciences, Anglia Ruskin University, East Road, Cambridge, CB1 1PT (United Kingdom); Scott, Karen [Forensic Medicine and Science, University of Glasgow, Glasgow G12 8QQ (United Kingdom); Harrison, Nancy [Life Sciences, Anglia Ruskin University, East Road, Cambridge, CB1 1PT (United Kingdom)

2011-05-15

Exposure to the nonsteroidal anti-inflammatory drug (NSAID) diclofenac resulted in the near extinction of three species of Gyps vultures on the Indian subcontinent. Other NSAIDs present in the environment, including flunixin, may pose a similar risk. In the course of a study to determine the feasibility of detecting NSAIDs in keratinous matrices (i.e., hair, nails and feathers) using GC-MS, wool opportunistically collected from a sheep treated with flunixin was analysed for residues. Flunixin was detected qualitatively in external wool wash and extract samples. While residues of veterinary agents and pesticides have previously been found in sheep's wool, our preliminary investigation provides the first instance of an NSAID being detected in this matrix. Here we provide the sample preparation methods and GC-MS parameters used to enable further refinement as part of ongoing conservation and consumer quality control measures. - Highlights: > In this study we qualitatively detected the NSAID flunixin in sheep's wool using GC-MS. > Potential applications of this technique to the conservation of avian scavengers are outlined. > The quantitative and confirmatory steps required to fully validate the method are also provided. - This is the first time that an NSAID has been investigated or detected in sheep's wool. As such, it details a novel exposure pathway for scavenging species in the environment and offers a potential tool for future monitoring effort in vulture conservation.

Dereplication of Natural Products Using GC-TOF Mass Spectrometry: Improved Metabolite Identification By Spectral Deconvolution Ratio Analysis

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Fausto Carnevale Neto

2016-09-01

Full Text Available Dereplication based on hyphenated techniques has been extensively applied in plant metabolomics, avoiding re-isolation of known natural products. However, due to the complex nature of biological samples and their large concentration range, dereplication requires the use of chemometric tools to comprehensively extract information from the acquired data. In this work we developed a reliable GC-MS-based method for the identification of non-targeted plant metabolites by combining the Ratio Analysis of Mass Spectrometry deconvolution tool (RAMSY with Automated Mass Spectral Deconvolution and Identification System software (AMDIS. Plants species from Solanaceae, Chrysobalanaceae and Euphorbiaceae were selected as model systems due to their molecular diversity, ethnopharmacological potential and economical value. The samples were analyzed by GC-MS after methoximation and silylation reactions. Dereplication initiated with the use of a factorial design of experiments to determine the best AMDIS configuration for each sample, considering linear retention indices and mass spectral data. A heuristic factor (CDF, compound detection factor was developed and applied to the AMDIS results in order to decrease the false-positive rates. Despite the enhancement in deconvolution and peak identification, the empirical AMDIS method was not able to fully deconvolute all GC-peaks, leading to low MF values and/or missing metabolites. RAMSY was applied as a complementary deconvolution method to AMDIS to peaks exhibiting substantial overlap, resulting in recovery of low-intensity co-eluted ions. The results from this combination of optimized AMDIS with RAMSY attested to the ability of this approach as an improved dereplication method for complex biological samples such as plant extracts.

Determinação de herbicidas usados no cultivo de arroz irrigado na região sul do estado de Santa Catarina através da SPME-GC-ECD Determination of herbicides used in irrigated rice cultivation in the south of Santa Catarina using SPME-GC-ECD

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Léa L. F. Costa

2008-01-01

Full Text Available Evaluation of the pollution by the herbicides alachlor, propanil and atrazine in water samples from four rivers in the cities of Turvo and Meleiro, south of Santa Catarina State, was made using the SPME-GC-ECD method. The proposed method was optimized and validated. The correlation coefficients were higher than 0.997 and linear ranges of the analytical curves were 0.1-4; 0.1-2.5 and 0.1-5 µg L-1 for atrazine, alachlor and propanil, respectively. The herbicides were quantified by GC-ECD and identified by GC-MS. Both of the selected rivers presented contamination by at least one of the studied herbicides.

Bioaccumulation study of acrylate monomers in algae (Chlorella Kessleri) by PY-GC and PY-GC/MS

International Nuclear Information System (INIS)

Halas, L.; Orinak, A.; Adamova, M.; Ladomersky, J.

2004-01-01

Acrylate monomers methylmethacrylate (MMA) and cyclohexylmethacrylate (CHMA) bioaccumulation has been determined in aquatic organism, algae (Chlorella kessleri). Algae were collected in amount of 0.4 mg and directly injected to the paralytic cell. In algae bodies accumulated monomers were analysed by pyrolysis gas chromatography (Py-GC) and pyrolysis gas chromatography coupled with mass spectrometry (Py-GC/MS). Traces of the accumulated monomers in algae body can be determined after 1-, 2 -, 3-weeks of incubation. Maximum content of MMA was determined after 3-week of experiment, contrariwise in the case of CHMA after 2-week exposition. Relationship with pyrolysis temperature has also been studied. (authors)

Measurement of HDO Products Using GC-TCD: Towards Obtaining Reliable Analytical Data

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Zuas Oman

2018-03-01

Full Text Available This paper reported the method development and validation of a gas chromatography with thermal conductivity detector (GC-TCD method for the measurement of the gaseous products of hydrodeoxygenation (HDO. The method validation parameters include selectivity, precision (repeatability and reproducibility, accuracy, linearity, limit of detection (LoD, limit of quantitation (LoQ, and robustness. The results showed that the developed method was able to separate the target components (H2, CO2, CH4 and CO from their mixtures without any special sample treatment. The validated method was selective, precise, accurate, and robust. Application of the developed and validated GC-TCD method to the measurement of by-product components of HDO of bio-oil revealed a good performance with relative standard deviation (RSD less than 1.0% for all target components, implying that the process of method development and validation provides a trustworthy way of obtaining reliable analytical data.

Fully Automated Trimethylsilyl (TMS Derivatisation Protocol for Metabolite Profiling by GC-MS

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Erica Zarate

2016-12-01

Full Text Available Gas Chromatography-Mass Spectrometry (GC-MS has long been used for metabolite profiling of a wide range of biological samples. Many derivatisation protocols are already available and among these, trimethylsilyl (TMS derivatisation is one of the most widely used in metabolomics. However, most TMS methods rely on off-line derivatisation prior to GC-MS analysis. In the case of manual off-line TMS derivatisation, the derivative created is unstable, so reduction in recoveries occurs over time. Thus, derivatisation is carried out in small batches. Here, we present a fully automated TMS derivatisation protocol using robotic autosamplers and we also evaluate a commercial software, Maestro available from Gerstel GmbH. Because of automation, there was no waiting time of derivatised samples on the autosamplers, thus reducing degradation of unstable metabolites. Moreover, this method allowed us to overlap samples and improved throughputs. We compared data obtained from both manual and automated TMS methods performed on three different matrices, including standard mix, wine, and plasma samples. The automated TMS method showed better reproducibility and higher peak intensity for most of the identified metabolites than the manual derivatisation method. We also validated the automated method using 114 quality control plasma samples. Additionally, we showed that this online method was highly reproducible for most of the metabolites detected and identified (RSD < 20 and specifically achieved excellent results for sugars, sugar alcohols, and some organic acids. To the very best of our knowledge, this is the first time that the automated TMS method has been applied to analyse a large number of complex plasma samples. Furthermore, we found that this method was highly applicable for routine metabolite profiling (both targeted and untargeted in any metabolomics laboratory.

Integrated cancer therapy combined radiotherapy and immunotherapy. The challenge of using Gc protein-derived macrophage activating factor (GcMAF) as a key molecule

International Nuclear Information System (INIS)

Uto, Yoshihiro; Hori, Hitoshi

2013-01-01

Radiation oncologists know the conflict between radiotherapy and immunotherapy, but now challenged trails of the integrative cancer therapies combined radiation therapy and various immunoreaction/immune therapies begin. We therefore review the recent results of basic research and clinical trial of the integrated cancer therapies which combined radiotherapy and various immune therapies/immunoreaction, and the challenged studies of combined use of radiotherapy and our developed cancer immunotherapy using serum GcMAF which is human serum containing Gc protein-derived macrophage activating factor (GcMAF). (author)

Highly Enhanced Photoreductive Degradation of Polybromodiphenyl Ethers with g-C3N4/TiO2 under Visible Light Irradiation

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Weidong Ye

2017-04-01

Full Text Available A series of high activity photocatalysts g-C3N4-TiO2 were synthesized by simple one-pot thermal transformation method and characterized by transmission electron microscopy (TEM, scanning electron microscopy (SEM, X-ray diffraction (XRD, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller (BET surface area, and ultraviolet–visible diffuse reflectance spectroscopy (UV-Vis-DRS. The g-C3N4-TiO2 samples show highly improved photoreductive capability for the degradation of polybromodiphenyl ethers compared with g-C3N4 under visible light irradiation. Among all the hybrids, 0.02-C3N4-TiO2 with 2 wt % g-C3N4 loaded shows the highest reaction rate, which is 15 times as high as that in bare g-C3N4. The well-matched band gaps in heterojunction g-C3N4-TiO2 not only strengthen the absorption intensity, but also show more effective charge carrier separation, which results in the highly enhanced photoreductive performance under visible light irradiation. The trapping experiments show that holetrapping agents largely affect the reaction rate. The rate of electron accumulation in the conductive band is the rate-determining step in the degradation reaction. A possible photoreductive mechanism has been proposed.

Optimization of the Extraction of the Volatile Fraction from Honey Samples by SPME-GC-MS, Experimental Design, and Multivariate Target Functions

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Elisa Robotti

2017-01-01

Full Text Available Head space (HS solid phase microextraction (SPME followed by gas chromatography with mass spectrometry detection (GC-MS is the most widespread technique to study the volatile profile of honey samples. In this paper, the experimental SPME conditions were optimized by a multivariate strategy. Both sensitivity and repeatability were optimized by experimental design techniques considering three factors: extraction temperature (from 50°C to 70°C, time of exposition of the fiber (from 20 min to 60 min, and amount of salt added (from 0 to 27.50%. Each experiment was evaluated by Principal Component Analysis (PCA that allows to take into consideration all the analytes at the same time, preserving the information about their different characteristics. Optimal extraction conditions were identified independently for signal intensity (extraction temperature: 70°C; extraction time: 60 min; salt percentage: 27.50% w/w and repeatability (extraction temperature: 50°C; extraction time: 60 min; salt percentage: 27.50% w/w and a final global compromise (extraction temperature: 70°C; extraction time: 60 min; salt percentage: 27.50% w/w was also reached. Considerations about the choice of the best internal standards were also drawn. The whole optimized procedure was than applied to the analysis of a multiflower honey sample and more than 100 compounds were identified.

An introduction to statistical computing a simulation-based approach

CERN Document Server

Voss, Jochen

2014-01-01

A comprehensive introduction to sampling-based methods in statistical computing The use of computers in mathematics and statistics has opened up a wide range of techniques for studying otherwise intractable problems.  Sampling-based simulation techniques are now an invaluable tool for exploring statistical models.  This book gives a comprehensive introduction to the exciting area of sampling-based methods. An Introduction to Statistical Computing introduces the classical topics of random number generation and Monte Carlo methods.  It also includes some advanced met

An Improvement on Space Focusing Resolution in Two-Field Time-of-Flight Mass Spectrometers

International Nuclear Information System (INIS)

Yildirim, M.; Aydin, R.; Akin, U.; Kilic, H. S.; Sise, O.; Ulu, M.; Dogan, M.

2007-01-01

Time-of-Flight Mass Spectrometer (TOFMS) is a sophisticated device for the mass selective analysis of a variety of samples. The main limitation on TOFMS technique is the obtainable resolution where the two main limiting factors are the initial space and energy spread of particles created in ionization region. Similar charged particles starting at different points will reach the detector at different times. So, this problem makes space focusing is very important subject. We have presented principles of two-fields TOFMS with second-order space focusing both using analytical methods and ray-tracing simulation. This work aims understanding of ion optical system clearly and gives hint of expectation for future developments

Surface modification of TiO2 with g-C3N4 for enhanced UV and visible photocatalytic activity

International Nuclear Information System (INIS)

Lei, Juying; Chen, Ying; Shen, Fan; Wang, Lingzhi; Liu, Yongdi; Zhang, Jinlong

2015-01-01

Highlights: • g-C 3 N 4 /TiO 2 was prepared by a one-step preparation under mild conditions. • Photocatalysts showed excellent activity under both UV and visible light. • A neat surface modification process is proved, excluding influence of N doping. • Two photocatalytic mechanisms under different wavelengths are proposed. • A wide range of available wavelengths would greatly improve practicability of TiO 2 . - Abstract: g-C 3 N 4 modified TiO 2 composites were prepared through a simple calcination process of anatase and cyanamide. The as-prepared samples were characterized by X-ray diffraction (XRD), diffuse reflectance spectrophotometry (DRS), fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), thermogravimetry differential thermal analysis (TG–DTA) and X-ray photoelectron spectroscopy (XPS), proving a successful modification of TiO 2 with g-C 3 N 4 . Photodegradation of acid orange 7 (AO7) was used to evaluate the photocatalytic activities of the composites, showing excellent activity of them under both visible and UV light. In addition, base treatment was then introduced to investigate the interaction between g-C 3 N 4 and TiO 2 . After removing the g-C 3 N 4 modified on TiO 2 by base, no nitrogen doping is found in TiO 2 lattice, demonstrating the g-C 3 N 4 was surface attached on TiO 2 and attributing all improvement of photocatalytic activity of g-C 3 N 4 /TiO 2 composite to the synergy between the two semiconductors

Passive Sampling and Analysis of Naphthalene in Internal Combustion Engine Exhaust with Retracted SPME Device and GC-MS

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Nassiba Baimatova

2017-07-01

Full Text Available Exhaust gases from internal combustion engines are the main source of urban air pollution. Quantification of Polycyclic aromatic hydrocarbons (PAHs in the exhaust gases is needed for emissions monitoring, enforcement, development, and testing of control technologies. The objective was to develop quantification of gaseous naphthalene in diesel engine exhaust based on diffusion-controlled extraction onto a retracted solid-phase microextraction (SPME fiber coating and analysis on gas chromatography-mass spectrometry (GC-MS. Extraction of naphthalene with retracted fibers followed Fick’s law of diffusion. Extracted mass of naphthalene was proportional to Cg, t, Dg, T and inversely proportional to Z. Method detection limit (p = 0.95 was 11.5 ppb (0.06 mg·m−3 at t = 9 h, Z = 10 mm and T = 40 °C, respectively. It was found that the % mass extracted of naphthalene by SPME needle assembly depended on the type of fiber. Storage time at different temperatures did not affect analyte losses extracted by polydimethylsiloxane (PDMS 100 µm fiber. The developed method was tested on exhaust gases from idling pickup truck and tractor, and compared side-by-side with a direct injection of sampled exhaust gas method. Time-weighted average (TWA concentrations of naphthalene in exhaust gases from idling pickup truck and a tractor ranged from 0.08 to 0.3 mg·m−3 (15.3–53.7 ppb.

Multi-platform metabolomics assays for human lung lavage fluids in an air pollution exposure study.

Science.gov (United States)

Surowiec, Izabella; Karimpour, Masoumeh; Gouveia-Figueira, Sandra; Wu, Junfang; Unosson, Jon; Bosson, Jenny A; Blomberg, Anders; Pourazar, Jamshid; Sandström, Thomas; Behndig, Annelie F; Trygg, Johan; Nording, Malin L

2016-07-01

Metabolomics protocols are used to comprehensively characterize the metabolite content of biological samples by exploiting cutting-edge analytical platforms, such as gas chromatography (GC) or liquid chromatography (LC) coupled to mass spectrometry (MS) assays, as well as nuclear magnetic resonance (NMR) assays. We have developed novel sample preparation procedures combined with GC-MS, LC-MS, and NMR metabolomics profiling for analyzing bronchial wash (BW) and bronchoalveolar lavage (BAL) fluid from 15 healthy volunteers following exposure to biodiesel exhaust and filtered air. Our aim was to investigate the responsiveness of metabolite profiles in the human lung to air pollution exposure derived from combustion of biofuels, such as rapeseed methyl ester biodiesel, which are increasingly being promoted as alternatives to conventional fossil fuels. Our multi-platform approach enabled us to detect the greatest number of unique metabolites yet reported in BW and BAL fluid (82 in total). All of the metabolomics assays indicated that the metabolite profiles of the BW and BAL fluids differed appreciably, with 46 metabolites showing significantly different levels in the corresponding lung compartments. Furthermore, the GC-MS assay revealed an effect of biodiesel exhaust exposure on the levels of 1-monostearylglycerol, sucrose, inosine, nonanoic acid, and ethanolamine (in BAL) and pentadecanoic acid (in BW), whereas the LC-MS assay indicated a shift in the levels of niacinamide (in BAL). The NMR assay only identified lactic acid (in BW) as being responsive to biodiesel exhaust exposure. Our findings demonstrate that the proposed multi-platform approach is useful for wide metabolomics screening of BW and BAL fluids and can facilitate elucidation of metabolites responsive to biodiesel exhaust exposure. Graphical Abstract Graphical abstract illustrating the study workflow. NMR Nuclear Magnetic Resonance, LC-TOFMS Liquid chromatography-Time Of Flight Mass Spectrometry, GC Gas

EIA and GC/MS analysis of 8-isoprostane in EBC of children with problematic asthma.

Science.gov (United States)

Carraro, S; Cogo, P E; Isak, I; Simonato, M; Corradi, M; Carnielli, V P; Baraldi, E

2010-06-01

Asthmatic airways are characterised by enhanced oxidative stress, which can be studied by measuring biomarkers, such as 8-isoprostane. The aims of the present study were: 1) to measure the concentrations of 8-isoprostane in exhaled breath condensate (EBC) and urine of children with problematic and well-controlled asthma; 2) to compare the concentrations of 8-isoprostane measured by gas chromatographic/negative ion chemical ionisation mass spectrometry (GC/NICI-MS) and by an enzymatic immunoassay (EIA). We recruited 20 asthmatic allergic children, 13 with well-controlled asthma and seven with problematic asthma. They underwent exhaled nitric oxide measurements and spirometry, and both EBC and urine samples were collected. 8-isoprostane was measured in EBC by GC/NICI-MS and EIA. 8-isoprostane concentrations in EBC were significantly higher in children with problematic asthma than in children with well-controlled asthma (p = 0.01). An acceptable reproducibility emerged between GC/NICI-MS and EIA (coefficient of reproducibility 11.5 pg x mL(-1)). 8-isoprostane levels measured in urine did not correlate with those measured in EBC. We showed that 8-isoprostane in EBC was significantly increased in children with problematic asthma, suggesting a role for oxidative stress in this asthma phenotype. In addition we found an acceptable reproducibility of EIA compared to GC/NICI-MS, even if the latter method had higher accuracy.

High GC content causes orphan proteins to be intrinsically disordered.

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Walter Basile

2017-03-01

Full Text Available De novo creation of protein coding genes involves the formation of short ORFs from noncoding regions; some of these ORFs might then become fixed in the population. These orphan proteins need to, at the bare minimum, not cause serious harm to the organism, meaning that they should for instance not aggregate. Therefore, although the creation of short ORFs could be truly random, the fixation should be subjected to some selective pressure. The selective forces acting on orphan proteins have been elusive, and contradictory results have been reported. In Drosophila young proteins are more disordered than ancient ones, while the opposite trend is present in yeast. To the best of our knowledge no valid explanation for this difference has been proposed. To solve this riddle we studied structural properties and age of proteins in 187 eukaryotic organisms. We find that, with the exception of length, there are only small differences in the properties between proteins of different ages. However, when we take the GC content into account we noted that it could explain the opposite trends observed for orphans in yeast (low GC and Drosophila (high GC. GC content is correlated with codons coding for disorder promoting amino acids. This leads us to propose that intrinsic disorder is not a strong determining factor for fixation of orphan proteins. Instead these proteins largely resemble random proteins given a particular GC level. During evolution the properties of a protein change faster than the GC level causing the relationship between disorder and GC to gradually weaken.

Correlation of rocket propulsion fuel properties with chemical composition using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry followed by partial least squares regression analysis.

Science.gov (United States)

Kehimkar, Benjamin; Hoggard, Jamin C; Marney, Luke C; Billingsley, Matthew C; Fraga, Carlos G; Bruno, Thomas J; Synovec, Robert E

2014-01-31

There is an increased need to more fully assess and control the composition of kerosene-based rocket propulsion fuels such as RP-1. In particular, it is critical to make better quantitative connections among the following three attributes: fuel performance (thermal stability, sooting propensity, engine specific impulse, etc.), fuel properties (such as flash point, density, kinematic viscosity, net heat of combustion, and hydrogen content), and the chemical composition of a given fuel, i.e., amounts of specific chemical compounds and compound classes present in a fuel as a result of feedstock blending and/or processing. Recent efforts in predicting fuel chemical and physical behavior through modeling put greater emphasis on attaining detailed and accurate fuel properties and fuel composition information. Often, one-dimensional gas chromatography (GC) combined with mass spectrometry (MS) is employed to provide chemical composition information. Building on approaches that used GC-MS, but to glean substantially more chemical information from these complex fuels, we recently studied the use of comprehensive two dimensional (2D) gas chromatography combined with time-of-flight mass spectrometry (GC×GC-TOFMS) using a "reversed column" format: RTX-wax column for the first dimension, and a RTX-1 column for the second dimension. In this report, by applying chemometric data analysis, specifically partial least-squares (PLS) regression analysis, we are able to readily model (and correlate) the chemical compositional information provided by use of GC×GC-TOFMS to RP-1 fuel property information such as density, kinematic viscosity, net heat of combustion, and so on. Furthermore, we readily identified compounds that contribute significantly to measured differences in fuel properties based on results from the PLS models. We anticipate this new chemical analysis strategy will have broad implications for the development of high fidelity composition-property models, leading to an

A high-throughput headspace gas chromatographic technique for the determination of nitrite content in water samples.

Science.gov (United States)

Zhang, Shu-Xin; Peng, Rong; Jiang, Ran; Chai, Xin-Sheng; Barnes, Donald G

2018-02-23

This paper reports on a high-throughput headspace gas chromatographic method (HS-GC) for the determination of nitrite content in water sample, based on GC measurement of cyclohexene produced from the reaction between nitrite and cyclamate in a closed vial. The method has a relative standard deviation of water samples. In short, the present HS-GC method is simple, accurate, and sensitive, and it is very suitable to be used in the batch sample testing. Copyright © 2018 Elsevier B.V. All rights reserved.

Taking the atmosphere's pulse: The application of GC-IRMS to stable isotopes in atmospheric trace gases

International Nuclear Information System (INIS)

Lowe, D.C.; Ferretti, D.J.; Francey, R.J.; Allison, C.E.

2001-01-01

Since the industrial revolution, the abundance of many atmospheric trace gases has changed significantly. This is of concern because many of these trace species play a fundamental role in determining physical and chemical properties of the atmosphere important for maintaining life on earth. The impacts of the changes have been studied by a combination of analytical and theoretical modelling techniques. Stable isotope measurements made by conventional dual inlet IRMS for example, have provided valuable constraints on the budgets and removal mechanisms of key atmospheric trace gases. Unfortunately, in most cases, the application of these methods has been limited, because large air samples and cumbersome off line processing techniques are required to pre-concentrate enough gas for analysis. GC-IRMS offers a very attractive alternative because it combines on line processing with air sample size requirements typically 1000 times less than used in conventional techniques. In this article we focus on the requirements imposed on GC-IRMS by some of the current applications in atmospheric trace gas research. In addition, we examine some of the analytical and calibration aspects of the method applied to this kind of work. We finish with a summary of some of the comparative advantages and disadvantages of the GC-IRMS technique and some suggestions for future research using the method applied to specific atmospheric trace gases. (author)

A simplified procedure for GC/C/IRMS analysis of underivatized 19-norandrosterone in urine following HPLC purification.

Science.gov (United States)

de la Torre, Xavier; Colamonici, Cristiana; Curcio, Davide; Molaioni, Francesco; Pizzardi, Marta; Botrè, Francesco

2011-04-01

Nandrolone and/or its precursors are included in the World Anti-doping Agency (WADA) list of forbidden substances and methods and as such their use is banned in sport. 19-Norandrosterone (19-NA) the main metabolite of these compounds can also be produced endogenously. The need to establish the origin of 19-NA in human urine samples obliges the antidoping laboratories to use isotope ratio mass spectrometry (IRMS) coupled to gas chromatography (GC/C/IRMS). In this work a simple liquid chromatographic method without any additional derivatization step is proposed, allowing to drastically simplify the urine pretreatment procedure, leading to extracts free of interferences permitting precise and accurate IRMS analysis. The purity of the extracts was verified by parallel analysis by gas chromatography coupled to mass spectrometry with GC conditions identical to those of the GC/C/IRMS assay. The method has been validated according to ISO17025 requirements (within assay precision of ±0.3‰ and between assay precision of ±0.4‰). The method has been tested with samples obtained after the administration of synthetic 19-norandrostenediol and samples collected during pregnancy where 19-NA is known to be produced endogenously. Twelve drugs and synthetic standards able to produce through metabolism 19-NA have shown to present δ(13)C values around -29‰ being quite homogeneous (-28.8±1.5; mean±standard deviation) while endogenously produced 19-NA has shown values comparable to other endogenous produced steroids in the range -21 to -24‰ as already reported. The efficacy of the method was tested on real samples from routine antidoping analyses. Copyright © 2011 Elsevier Inc. All rights reserved.

Concurrent Lactic and Volatile Fatty Acid Analysis of Microbial Fermentation Samples by Gas Chromatography with Heat Pre-treatment.

Science.gov (United States)

Darwin; WipaCharles; Cord-Ruwisch, Ralf

2018-01-01

Organic acid analysis of fermentation samples can be readily achieved by gas chromatography (GC), which detects volatile organic acids. However, lactic acid, a key fermentation acid is non-volatile and can hence not be quantified by regular GC analysis. However the addition of periodic acid to organic acid samples has been shown to enable lactic acid analysis by GC, as periodic acid oxidizes lactic acid to the volatile acetaldehyde. Direct GC injection of lactic acid standards and periodic acid generated inconsistent and irreproducible peaks, possibly due to incomplete lactic acid oxidation to acetaldehyde. The described method is developed to improve lactic acid analysis by GC by using a heat treated derivatization pre-treatment, such that it becomes independent of the retention time and temperature selection of the GC injector. Samples containing lactic acid were amended by periodic acid and heated in a sealed test tube at 100°C for at least 45 min before injecting it to the GC. Reproducible and consistent peaks of acetaldehyde were obtained. Simultaneous determination of lactic acid, acetone, ethanol, butanol, volatile fatty acids could also be accomplished by applying this GC method, enabling precise and convenient organic acid analysis of biological samples such as anaerobic digestion and fermentation processes. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Seasonal variation and source estimation of organic compounds in urban aerosol of Augsburg, Germany

International Nuclear Information System (INIS)

Pietrogrande, Maria Chiara; Abbaszade, Guelcin; Schnelle-Kreis, Juergen; Bacco, Dimitri; Mercuriali, Mattia; Zimmermann, Ralf

2011-01-01

This study reports a general assessment of the organic composition of the PM 2.5 samples collected in the city of Augsburg, Germany in a summer (August-September 2007) and a winter (February-March 2008) campaign of 36 and 30 days, respectively. The samples were directly submitted to in-situ derivatisation thermal desorption gas chromatography coupled with time of flight mass spectrometry (IDTD-GC-TOFMS) to simultaneously determine the concentrations of many classes of molecular markers, such as n-alkanes, iso- and anteiso-alkanes, polycyclic aromatic hydrocarbons (PAHs), oxidized PAHs, n-alkanoic acids, alcohols, saccharides and others. The PCA analysis of the data identified the contributions of three emission sources, i.e., combustion sources, including fossil fuel emissions and biomass burning, vegetative detritus, and oxidized PAHs. The PM chemical composition shows seasonal trend: winter is characterized by high contribution of petroleum/wood combustion while the vegetative component and atmospheric photochemical reactions are predominant in the hot season. - Highlights: → 59 molecular markers were simultaneously determined by thermal desorption GC-MS. → Organic composition of urban PM 2.5 in Augsburg, Germany, was characterized. → Fossil fuel, vegetative detritus, coal/wood burning are the main sources. → Seasonal trends winter vs. summer were identified. - Organic composition of the urban PM 2.5 identifies seasonal trend of the main sources: fossil fuel and biomass combustion sources, vegetative detritus, atmospheric photochemical reactions.

Determination of pesticides in fruits and vegetables using acetonitrile extraction and GC/MS technique

International Nuclear Information System (INIS)

Hussain, Z.

2010-01-01

A selection of oranges, guava and spinach were purchased from the local markets of Lahore, Pakistan. Extraction of the samples was carried out using an acetonitrile/toluene extraction procedure to determine the residual concentration of pesticides which may have been used during seasonal growth. Gas chromatography/mass spectrometry (GC/MS) was used for quantitative and confirmatory analysis of GC-amenable pesticides. The data obtained was compared with that of a referenced pesticide by matching molecular weight to a library of known pesticides. For comparison the same non-sprayed fruits/vegetable were extracted as a control reference. Factors studied were retention time, elution time, relative abundance and molecular weight. The results showed that low molecular weight pesticides were eluted before the high molecular weight pesticides. Pesticides identified included crotoxyphos, fenoxycarb and methoxyfenozide. (author)

"Detection of Morphine in Opioid Abusers Hair by GC/MS "

Directory of Open Access Journals (Sweden)

Khosrou Abdi

2004-07-01

Full Text Available Thirty hair samples were collected from the male opioid abusers in which the presence of morphine in their urine samples was confirmed by Thin Layer Chromatography (TLC analyses. The hair samples were washed, cut into small pieces and extracted in a mixture of methanol-triflouroacetic acid (9:1. The methanolic phase was evaporated to dryness under nitrogen stream and derivitized by addition of N-methyl-N-trimethylsilyl triflouroacetamide (MSTFA and 1% trimethyl iodosilane (TMIS with sonication. One micro liter of each derivitized sample was injected into a Gas Chromatograph-Mass Spectrometer (GC/MS system consisting of a capillary column and finnigan MS with selective ion monitoring (SIM mode. The selected mass for ions codeine and morphine were 370 and 429, respectively. The limit of detection (LOD was set at 0.03ng/mg of the hair. By using the above procedure, morphine was detectable in all of the examined samples and this method is capable to detec low levels of morphine in hair for a long period of time following the last intake of the drug

An introduction to automatic radioactive sample counters

International Nuclear Information System (INIS)

1980-01-01

The subject is covered in chapters, entitled; the detection of radiation in sample counters; nucleonic equipment; liquid scintillation counting; basic features of automatic sample counters; statistics of counting; data analysis; purchase, installation, calibration and maintenance of automatic sample counters. (U.K.)

High-performance for hydrogen evolution and pollutant degradation of reduced graphene oxide/two-phase g-C3N4 heterojunction photocatalysts.

Science.gov (United States)

Song, Chengjie; Fan, Mingshan; Shi, Weidong; Wang, Wei

2018-05-01

We have successfully synthesized the composites of two-phase g-C 3 N 4 heterojunction photocatalysts by one-step method. And the reduced graphene oxide/two-phase g-C 3 N 4 heterojunction photocatalyst was fabricated via a facile hydrothermal reduction method. The characterization results indicated that the two-phase g-C 3 N 4 was integrated closely, and the common phenomenon of agglomeration for g-C 3 N 4 was significantly reduced. Moreover, the oxidized graphene was reduced successfully in the composites and the graphene was overlaid on the surface or the interlayers of g-C 3 N 4 heterojunction composite uniformly. In addition, we have carried out the photocatalytic activity experiments by H 2 evolution and rhodamine B removal, tetracycline removal under the visible light irradiation. The results revealed that the composite has improved the separation efficiency a lot than the pure photocatalyst. The photocurrent test demonstrated that the recombination of electrons and holes were efficiently inhibited as well as enhanced the photocatalytic activity. The 0.4% rGO loaded samples, 0.4% rGOCN2, own the best performance. Its rate of H 2 evolution was 15 times as high as that of the pure g-C 3 N 4 .

Differential GC Content between Exons and Introns Establishes Distinct Strategies of Splice-Site Recognition

Directory of Open Access Journals (Sweden)

Maayan Amit

2012-05-01

Full Text Available During evolution segments of homeothermic genomes underwent a GC content increase. Our analyses reveal that two exon-intron architectures have evolved from an ancestral state of low GC content exons flanked by short introns with a lower GC content. One group underwent a GC content elevation that abolished the differential exon-intron GC content, with introns remaining short. The other group retained the overall low GC content as well as the differential exon-intron GC content, and is associated with longer introns. We show that differential exon-intron GC content regulates exon inclusion level in this group, in which disease-associated mutations often lead to exon skipping. This group's exons also display higher nucleosome occupancy compared to flanking introns and exons of the other group, thus “marking” them for spliceosomal recognition. Collectively, our results reveal that differential exon-intron GC content is a previously unidentified determinant of exon selection and argue that the two GC content architectures reflect the two mechanisms by which splicing signals are recognized: exon definition and intron definition.

Safety, immunogenicity, and early evidence of antitumor response with the use of the vaccine formulation NeuGcGM3 / VSSPs in patients with advanced melanoma

International Nuclear Information System (INIS)

Osorio Rodríguez, Marta de la Caridad

2014-01-01

Introduction. Melanoma is now considered an epidemic around the world. Its high lethality, constitutes a serious problem despite the continuous pharmacological and technological advances. NeuGcGM3/VSSP is a vaccine formulation containing ganglioside NeuGcGM3 incorporated in the acting of Neisseria meningitidis. It may be a choice therapeutic given this ganglioside in primary melanoma expression and immunogenicity and safety demonstrated by this vaccine in advanced breast cancer. This study evaluated the safety, immunogenicity and the anti-tumor response in patients with advanced melanoma to manage it via IM or SC. Material and methods: The expression of ganglioside in primary melanomas and its metastases was identified by immunohistochemical methods with the AcM 14F7 (anti-NGCGM3). 2 clinical trials Phase Ib/IIa escalation of doses with NeuGcGM3 /VSSP were conducted in patients with melanoma Advanced IM and SC routes. Safety and anti-tumour response were evaluated with the CTC and RECIST criteria. The statistical analysis was performed with the SPSS statistical package. Results: NeuGcGM3 is expressed in primary tumors and the studied lymph nodes metastases. NeuGcGM3/VSSP was safely managed by the SC and IM, roads without limiting toxicity. Immunogenic with IgM and IgG isotype antibody response resulted in 75% patients. There was anti-tumoral response in 38.5% with increase in median SV mainly associated with anti-tumor response. The appearance of vitiligo and the response of antibodies against other not present in the vaccine formulation gangliosides may be considered a manifestation of immune restoration. Conclusions. NeuGcGM3/VSSP managed IM and SC in patients with advanced melanoma was safe, immunogenic and antitumor activity associated with overall survival advantage. (author)

Solid phase extraction of large volume of water and beverage samples to improve detection limits for GC-MS analysis of bisphenol A and four other bisphenols.

Science.gov (United States)

Cao, Xu-Liang; Popovic, Svetlana

2018-01-01

Solid phase extraction (SPE) of large volumes of water and beverage products was investigated for the GC-MS analysis of bisphenol A (BPA), bisphenol AF (BPAF), bisphenol F (BPF), bisphenol E (BPE), and bisphenol B (BPB). While absolute recoveries of the method were improved for water and some beverage products (e.g. diet cola, iced tea), breakthrough may also have occurred during SPE of 200 mL of other beverages (e.g. BPF in cola). Improvements in method detection limits were observed with the analysis of large sample volumes for all bisphenols at ppt (pg/g) to sub-ppt levels. This improvement was found to be proportional to sample volumes for water and beverage products with less interferences and noise levels around the analytes. Matrix effects and interferences were observed during SPE of larger volumes (100 and 200 mL) of the beverage products, and affected the accurate analysis of BPF. This improved method was used to analyse bisphenols in various beverage samples, and only BPA was detected, with levels ranging from 0.022 to 0.030 ng/g for products in PET bottles, and 0.085 to 0.32 ng/g for products in cans.

Volatiles from a rare Acer spp. honey sample from Croatia.

Science.gov (United States)

Jerković, Igor; Marijanović, Zvonimir; Malenica-Staver, Mladenka; Lusić, Drazen

2010-06-24

A rare sample of maple (Acer spp.) honey from Croatia was analysed. Ultrasonic solvent extraction (USE) using: 1) pentane, 2) diethyl ether, 3) a mixture of pentane and diethyl ether (1:2 v/v) and 4) dichloromethane as solvents was applied. All the extracts were analysed by GC and GC/MS. The most representative extracts were 3) and 4). Syringaldehyde was the most striking compound, being dominant in the extracts 2), 3) and 4) with percentages 34.5%, 33.1% and 35.9%, respectively. In comparison to USE results of other single Croatian tree honey samples (Robinia pseudoacacia L. nectar honey, Salix spp. nectar and honeydew honeys, Quercus frainetto Ten. honeydew as well as Abies alba Mill. and Picea abies L. honeydew) and literature data the presence of syringaldehyde, previously identified in maple sap and syrup, can be pointed out as a distinct characteristic of the Acer spp. honey sample. Headspace solid-phase microextraction (HS-SPME) combined with GC and GC/MS identified benzaldehyde (16.5%), trans-linalool oxide (20.5%) and 2-phenylethanol (14.9%) as the major compounds that are common in different honey headspace compositions.

Reduction of measurement uncertainty by experimental design in high-order (double, triple, and quadruple) isotope dilution mass spectrometry: application to GC-MS measurement of bromide.

Science.gov (United States)

Pagliano, Enea; Mester, Zoltán; Meija, Juris

2013-03-01

Since its introduction a century ago, isotope dilution analysis has played a central role in developments of analytical chemistry. This method has witnessed many elaborations and developments over the years. To date, we have single, double, and even triple isotope dilution methods. In this manuscript, we summarize the conceptual aspects of isotope dilution methods and introduce the quadruple dilution and the concept of exact matching triple and quadruple dilutions. The comparison of isotope dilution methods is performed by determination of bromide ions in groundwater using novel ethyl-derivatization chemistry in conjunction with GC/MS. We show that the benefits of higher-order isotope dilution methods are countered with a greater need for careful experimental design of the isotopic blends. Just as for ID(2)MS, ID(3)MS and ID(4)MS perform best when the isotope ratio of one sample/spike blend is matched with that of a standard/spike blend (exact matching).

Fatty Acid Detection in Mars-Analogous Rock Samples with the TMAH Wet Chemistry Experiment on the Sample Analysis at Mars (SAM) Instrument

Science.gov (United States)

Williams, A. J.; Eigenbrode, J. L.; Wilhelm, M. B.; Johnson, S. S.; Craft, K.; O'Reilly, S.; Lewis, J. M. T.; Williams, R.; Summons, R. E.; Benison, K. C.; Mahaffy, P. R.

2017-12-01

The Curiosity rover is exploring sedimentary rock sequences in Gale Crater for evidence of habitability and searching for organic compounds using the Sample Analysis at Mars (SAM) instrument suite. SAM includes a gas chromatograph mass spectrometer (GC-MS) and pyrolysis ovens. SAM has the ability to perform wet chemistry experiments, one of which uses tetramethylammonium hydroxide (TMAH) thermochemolysis to liberate bound lipids, making them sufficiently volatile for detection by GC-MS. To determine the effectiveness of the SAM-like TMAH experiment on fatty acid methyl ester (FAME) biomarker identification, rock and sediment samples were collected from a variety of Mars analog environments including iron oxides from a modern mineral precipitate and older surface gossan at Iron Mountain, CA, as well as modern acid salt and neutral lake sediments with mixed iron oxides and clays from Western Australia; siliceous sinter from recently inactive and modern near-vent Icelandic hot springs deposits; modern carbonate ooids from The Bahamas, and organic-rich shale from Germany. Samples underwent pyrolysis with TMAH. Fatty acids were analyzed by pyro-GC-MS using a SAM-like heating ramp (35°C/min) as well as a 500°C flash on a Frontier pyrolyzer and Agilent GC-MS instrument. Results reveal that FAMEs were detectable with the TMAH experiment in nearly all samples. Low molecular weight (MW) C6:0-C10:0 FAMEs were present in all samples, medium MW C11:0-C18:2 FAMEs were present in select samples, and high MW (HMW) C20:0-C30:0 FAMEs were present in the shale sample. Many of these samples exhibited an even-over-odd carbon number preference, indicating biological production. These experiments demonstrate that TMAH thermochemolysis with SAM-like pyro-GC-MS is effective in fatty acid analysis from natural Mars-analog samples that vary in mineralogy, age, and microbial community input. HMW FAMEs are not detected in iron-dominated samples, and may not be detectable at low

Statistics a biomedical introduction

CERN Document Server

Brown, Byron Wm

2009-01-01

CHAPTER 1: Introduction 1 CHAPTER 2: Elementary Rules of Probability 13 CHAPTER 3: Populations, Samples, and the Distribution of the Sample Mean 37 1. Populations and Distributions 38 2. Sampling from Finite Populations 64 3. The Distribution of the Sample Mean 72 CHAPTER 4: Analysis of Matched Pairs Using Sample Means 85 1. A Confidence Interval for the Treatment Effect 86 2. A Hypothesis Test for the Treatment Effect 96 3. Determining the Sample Size 102 CHAPTER 5: Analysis of the Two-Sample Location Problem Using Sample Means 109 1. A Confidence Interval for the Diffe

Polimorfisme gen ferroportin (FPN1 -1355 G/C sebagai faktor risiko anemia defisiensi besi pada ibu hamil

Directory of Open Access Journals (Sweden)

Nor Istiqomah

2013-04-01

Full Text Available Background: According to WHO data, prevalence of anemia pregnancy in Indonesia is 44.3%, it’s higher than world prevalence (41.8%. Ferroportin (FPN1 is one of important iron exsporter for iron absorption, release, and recycle inside the body. The varian of FPN1-1355 G/C in promoter region, leads to increased of ferroportin expression and iron export, increased cellular iron needs, overexpression of soluble transferrin receptor (sTfR, decrease hemoglobin (Hb and erythrocyte indices that manifest to iron deficiency anemia (IDA. Objective: This research will study the frequency of FPN1-1355 G/C polymorphism as a risk factor of IDA in pregnant women in Indonesia. Method: The research design was a case and control study. Blood samples were taken from 26 pregnant women with anemia and 48 pregnant women without anemia. FPN1-1355G/C polymorphism were determined using PCR-RFLP method. sTfR and ferritin level were measured with ELISA. Hemoglobin, erythrocyte indices, and sTfR level were compared among genotype group, then statistically analyzed using independent sample t-test and one way ANOVA. Bivariat analysis of Pearson test was conducted to analyze correlation between level of blood Hb and ferritin in pregnant women (p0.05. The sTfR and hepcidin level in subjects carrying C allele were higher than subjects carrying only G allele (p<0.05. Conclusion: In this study the FPN1 gene promoter -1355 G/C polymorphism was not a risk factor for anemia, but it was a risk factor for iron deficiency anemia in pregnant women.

Soil organic matter chemistry changes upon secondary succession in Imperata Grasslands , Indonesia: A pyrolysis - GC/MS study

NARCIS (Netherlands)

Yassir, I.; Buurman, P.

2012-01-01

The chemical composition of soil organic matter (SOM) following secondary succession in Imperata grassland was investigated by Pyrolysis-Gas Chromatography/Mass Spectrometry (GC/MS). We studied 46 samples from different stages of succession using plots that last burned 3 and 9 years previously,

Sol-gel titania-coated needles for solid phase dynamic extraction-GC/MS analysis of desomorphine and desocodeine.

Science.gov (United States)

Su, Chi-Ju; Srimurugan, Sankarewaran; Chen, Chinpiao; Shu, Hun-Chi

2011-01-01

Novel sol-gel titania film coated needles for solid-phase dynamic extraction (SPDE)-GC/MS analysis of desomorphine and desocodeine are described. The high thermal stability of titania film permits efficient extraction and analysis of poorly volatile opiate drugs. The influences of sol-gel reaction time, coating layer, extraction and desorption time and temperature on the SPDE needle performance were investigated. The deuterium labeled internal standard was introduced either during the extraction of analyte or directly injected to GC after the extraction process. The latter method was shown to be more sensitive for the analysis of water and urine samples containing opiate drugs. The proposed conditions provided a wide linear range (from 5-5000 ppb), and satisfactory linearity, with R(2) values from 0.9958 to 0.9999, and prominent sensitivity, LOQs (1.0-5.0 ng/g). The sol-gel titania film coated needle with SPDE-GC/MS will be a promising technique for desomorphine and desocodeine analysis in urine.

Construction of g-C_3N_4/Al_2O_3 hybrids via in-situ acidification and exfoliation with enhanced photocatalytic activity

International Nuclear Information System (INIS)

Wang, Xiao-jing; Liu, Chao; Li, Xu-li; Li, Fa-tang; Li, Yu-pei; Zhao, Jun; Liu, Rui-hong

2017-01-01

Highlights: • Ultrathin g-C_3N_4/Al_2O_3 hybrids are prepared via in-situ reaction. • The structure modification role of in-situ formed HNO_3 for g-C_3N_4 is found. • The ultrathin g-C_3N_4 nanosheets are formed by the acidified melamine and Al(OH)_3. • In-situ calcination of melamine and Al(OH)_3 benefits the contact of C_3N_4 and Al_2O_3. • The activity of g-C_3N_4/Al_2O_3 is 16.6 times that of pristine g-C_3N_4 in degrading RhB. - Abstract: Homogeneous ultrathin g-C_3N_4 nanosheets/Al_2O_3 heterojunctions are synthesized using melamine and Al(NO_3)_3 via in-situ reaction and the following thermal polymerization approach. The in-situ reaction between melamine and Al(NO_3)_3 results in the existence of HNO_3-acidified melamine and Al(OH)_3 aggregates via the hydrolysis of Al(NO_3)_3. After thermal polymerization, the aggregates are converted to g-C_3N_4/Al_2O_3 composites. The thermal polymerization of acidified melamine and the support effect of aluminum hydroxide for g-C_3N_4 during the calcination process lead to highly dispersed amrophous Al_2O_3 on ultrathin g-C_3N_4 nanosheets, which is beneficial for the separation of photogenerated electron-hole pairs in the heterojunction. The degradation rate for Rhodamine B (RhB) over the most activie sample is 16.6 times than that of pristine g-C_3N_4 under visible light irradiation, which can be attributed to the high specific surface area, highly dispersion of amorphous Al_2O_3 on ultrathin g-C_3N_4 nanosheet, and the effective electrons transfer from g-C_3N_4 to the amorphous Al_2O_3.

A fatal poisoning involving 2-fluorofentanyl

DEFF Research Database (Denmark)

Andreasen, Mette Findal; Hardlei, Tore Forsingdal; Rosendal, Ingrid

Background/introduction: A fatal intoxication involving 2-fluorofentanyl, a potent synthetic opioid analgesic, is reported. This is the first serious case associated with 2-fluorofentanyl that to our knowledge have been reported. 2-fluorofentanyl is the common name for N-(2-fluorophenyl)-N-[1...... and gastric content samples were submitted for toxicological examination; all samples were screened by ultra-performance liquid chromatography high-resolution time-of-flight mass spectrometry (UPLC-HR-TOFMS) and quantified by specific UPLC-MS/MS methods. Powder recovered from the scene of death was identified......-mortem femoral blood concentrations found were: 2-fluorofentanyl 0.012 mg/kg (UPLC-MS/MS); alcohol production as the body was moderate decomposed; buprenorphine 0.0004 mg/kg (UPLC-MS/MS) prescribed; quetiapine 0.088 mg/kg (UPLC-MS/MS) prescribed; venlafaxine 0.089 mg...

Determination of fatty acids and volatile compounds in fruits of rosehip(Rosa L.) species by HS-SPME/GC-MS and Im-SPME/GC-MS techniques

OpenAIRE

MURATHAN, ZEHRA TUĞBA; ZARIFIKHOSROSHAHI, MOZGAN; KAFKAS, NESİBE EBRU

2016-01-01

In this study, we aimed to compare fatty acid and volatile compound compositions of four rosehip species, namely Rosa pimpinellifolia, R. Villosa, R. Canina, and R. Dumalis, by gas chromatography with flame ionization detector (GC/FID) and headspace and immersion solid-phase microextraction gas chromatography-mass spectrometry (HS-SPME/GC-MS and Im-SPME/GC-MS) techniques. The total lipid contents in fruits of the rosehip species varied from 5.83% (R. Villosa) to 7.84% (R. Dumalis). A total of...

Non-steroidal anti-inflammatory drugs in the watercourses of Elbe basin in Czech Republic

Czech Academy of Sciences Publication Activity Database

Maršík, Petr; Rezek, Jan; Židková, Monika; Kramulová, Barbora; Tauchen, J.; Vaněk, Tomáš

2017-01-01

Roč. 171, MAR (2017), s. 97-105 ISSN 0045-6535 R&D Projects: GA ČR(CZ) GA14-22593S Grant - others:European Regional Development Fund(XE) CZ.2.16/3.1.00/24014; European Regional Development Fund(XE) CZ.2.16/3.1.00/21519 Institutional support: RVO:61389030 Keywords : chromatography-mass-spectrometry * gas-chromatography * human pharmaceuticals * waste-water * surface-water * risk-assessment * diclofenac * ibuprofen * products * plants * NSAID Surface water * Pharmaceuticals * GCxGC-TOFMS Elbe basin * Czech Republic Subject RIV: CE - Biochemistry OBOR OECD: Environmental biotechnology Impact factor: 4.208, year: 2016

Evaluation of HLA-G 14 bp Ins/Del and +3142G>C Polymorphism with Susceptibility and Early Disease Activity in Rheumatoid Arthritis

Directory of Open Access Journals (Sweden)

Mohammad Hashemi

2016-01-01

Full Text Available Purpose/Background. Mounting evidence designates that HLA-G plays a role in the regulation of inflammatory processes and autoimmune diseases. There are controversial reports concerning the impact of HLA-G gene polymorphism on rheumatoid arthritis (RA. This study was aimed at examining the impact of 14 bp ins/del and +3142G>C polymorphism with susceptibility and early disease activity in RA patients in a sample of the Iranian population. Methods. This case-control study was done on 194 patients with RA and 158 healthy subjects. The HLA-G rs1063320 (+3142G>C and rs66554220 (14 bp ins/del variants were genotype by polymerase chain reaction-restriction fragment length polymorphism (PCR-RFP and PCR method, respectively. Results. The HLA-G +3142G>C polymorphism significantly decreased the risk of RA in codominant (OR = 0.61, 95% CI = 0.38–0.97, p=0.038, GC versus GG; OR = 0.36, 95% CI = 0.14–0.92, p=0.034, CC versus GG, dominant (OR = 0.56, 95% CI = 0.36–0.87, p=0.011, GC + CC versus GG, and allele (OR = 0.58, 95% CI = 0.41–0.84, p=0.004, C versus G inheritance models tested. Our finding did not support an association between HLA-G 14 bp ins/del variant and risk/protection of RA. In addition, no significant association was found between the polymorphism and early disease activity. Conclusion. In summary, our results showed that HLA-G +3142G>C gene polymorphism significantly decreased the risk of RA in a sample of the Iranian population.

A combined XAFS, ESI TOF-MS and LIBD study on the formation of polynuclear Zr(IV), Th(IV) and Pu(IV) species

Science.gov (United States)

Rothe, J.; Walther, C.; Brendebach, B.; Büchner, S.; Fuss, M.; Denecke, M. A.; Geckeis, H.

2009-11-01

The long term radiotoxicity of spent nuclear fuel disposed of in deep underground repositories after discharge from nuclear power reactors is determined by actinide elements, mainly plutonium. Water intrusion into the repository might cause container corrosion and leaching of the waste matrices, leading to the release of Pu and other actinides into the geological environment. Performance assessment for a future nuclear waste repository requires detailed knowledge on actinide aqueous chemistry in the aquifer surrounding the disposal site. Tetravalent actinides exhibit a strong tendency towards hydrolysis and subsequent polymerization and/or colloid formation. These species provide a potential pathway for migration of actinides away from the repository. Therefore, it is of fundamental interest to study their generation and properties in-situ. To this end, X-ray Absorption Fine Structure Spectroscopy (XAFS) at the INE-Beamline for actinide research at ANKA, Electrospray Mass-Spectrometry (ESI TOF-MS) and Laser Induced Breakdown Detection (LIBD) are combined at FZK-INE in a comprehensive attempt to characterize Zr(IV) (An(IV) analogue), Th(IV) and Pu(IV) polymerization and colloid formation.

Forensic Drug Identification, Confirmation, and Quantification Using Fully Integrated Gas Chromatography with Fourier Transform Infrared and Mass Spectrometric Detection (GC-FT-IR-MS).

Science.gov (United States)

Lanzarotta, Adam; Lorenz, Lisa; Voelker, Sarah; Falconer, Travis M; Batson, JaCinta S

2018-05-01

This manuscript is a continuation of a recent study that described the use of fully integrated gas chromatography with direct deposition Fourier transform infrared detection and mass spectrometric detection (GC-FT-IR-MS) to identify and confirm the presence of sibutramine and AB-FUBINACA. The purpose of the current study was to employ the GC-FT-IR portion of the same instrument to quantify these compounds, thereby demonstrating the ability to identify, confirm, and quantify drug substances using a single GC-FT-IR-MS unit. The performance of the instrument was evaluated by comparing quantitative analytical figures of merit to those measured using an established, widely employed method for quantifying drug substances, high performance liquid chromatography with ultraviolet detection (HPLC-UV). The results demonstrated that GC-FT-IR was outperformed by HPLC-UV with regard to sensitivity, precision, and linear dynamic range (LDR). However, sibutramine and AB-FUBINACA concentrations measured using GC-FT-IR were not significantly different at the 95% confidence interval compared to those measured using HPLC-UV, which demonstrates promise for using GC-FT-IR as a semi-quantitative tool at the very least. The most significant advantage of GC-FT-IR compared to HPLC-UV is selectivity; a higher level of confidence regarding the identity of the analyte being quantified is achieved using GC-FT-IR. Additional advantages of using a single GC-FT-IR-MS instrument for identification, confirmation, and quantification are efficiency, increased sample throughput, decreased consumption of laboratory resources (solvents, chemicals, consumables, etc.), and thus cost.

Probability an introduction with statistical applications

CERN Document Server

Kinney, John J

2014-01-01

Praise for the First Edition""This is a well-written and impressively presented introduction to probability and statistics. The text throughout is highly readable, and the author makes liberal use of graphs and diagrams to clarify the theory.""  - The StatisticianThoroughly updated, Probability: An Introduction with Statistical Applications, Second Edition features a comprehensive exploration of statistical data analysis as an application of probability. The new edition provides an introduction to statistics with accessible coverage of reliability, acceptance sampling, confidence intervals, h

Direct calibration of GC/MS systems using SRM (Standard Reference Material) gas cylinders. Project report, January 1984-August 1985

International Nuclear Information System (INIS)

Byrd, G.D.; Richie, K.L.; Sniegoski, L.T.; White, E.

1985-10-01

A cryogenic trapping system has been developed for use in calibrating GC/MS systems for the analysis of volatile organic compounds. This system provides for direct Standard Reference Material (SRM) traceability on data generated on gaseous samples. The cryogenic trap is a coil of stainless steel tubing immersed in a cryogen to trap and preconcentrate organic species present in a gaseous sample. The trap also contains a heated injection port for the addition of isotopically labeled compounds for use in isotope dilution measurements. The first part of this research is concerned with the development of IDMS as an independent method for the quantification of analytes in gaseous samples to be used as standards. Results are presented for the determination of bromobenzene in nitrogen at nominal concentrations of 1 and 25 ppb. In the second part of the research, a calibration curve method was developed for using these standards in auditing the performance of GC/MS systems

Evaluation of false positive responses by mass spectrometry and ion mobility spectrometry for the detection of trace explosives in complex samples

Energy Technology Data Exchange (ETDEWEB)

Crawford, C.L., E-mail: clcrawf@sandia.gov; Hill, H.H.

2013-09-17

Graphical abstract: -- Highlights: •First study to use (−)SESI-IM-TOFMS to analyze complex mixtures of personal care products. •The study demonstrated, by identifying mobility and mass interferents with explosive signatures, which, if used separately, neither IMS nor MS alone would prevent every false positive for explosives when detected in the presence of a complex sample matrix. •Ingredients in common household cleaning products were shown to either enhance or suppress the ionization of explosives in a SESI-IM-TOFMS analysis. •Mobility separation provided real-time separation of ion species that indicated overlapping isotope peak patterns -- Abstract: Secondary electrospray ionization-ion mobility-time of flight mass spectrometry (SESI-IM-TOFMS) was used to evaluate common household products and food ingredients for any mass or mobility responses that produced false positives for explosives. These products contained ingredients which shared the same mass and mobility drift time ranges as the analyte ions for common explosives. The results of this study showed that the vast array of compounds in these products can cause either mass or mobility false positive responses. This work also found that two ingredients caused either enhanced or reduced ionization of the target analytes. Another result showed that an IMS can provide real-time separation of ion species that impede accurate mass identifications due to overlapping isotope peak patterns. The final result of this study showed that, when mass and mobility values were used to identify an ion, no false responses were found for the target explosives. The wider implication of these results is that the possibility exists for even greater occurrences of false responses from complex mixtures found in common products. Neither IMS nor MS alone can provide 100% assurance from false responses. IMS, due to its low cost, ease of operation, rugged reliability, high sensitivity and tunable selectivity, will remain

Enhancement of acid treated g-C3N4sbnd Cu2O photocatalytic activity by PEG under visible light irradiation

Science.gov (United States)

Zuo, Shiyu; Xu, Haiming; Liao, Wei; Sun, Lei; Li, Qiang; Zan, Jie; Zhang, Binyang; Li, Dongya; Xia, Dongsheng

2018-05-01

In this study, g-C3N4sbnd Cu2O was successfully synthesized in the presence of PEG-400 surfactant via an acid treatment hydrothermal method and a high-temperature calcination method. The structures and properties of as-synthesized samples were characterized using a range of techniques, such as XPS, TEM, PL and BET. The g-C3N4sbnd Cu2O heterojunction exhibits the enhanced photocatalytic performance and high stability. It is revealed that the addition of PEG can promote the heterojunction effect of g-C3N4sbnd Cu2O, effectively improving the crystallinity and specific surface area of the photocatalyst, separation efficiency of photocarriers, and light absorption, thus enhancing the photocatalytic performance.

Effect of water content on thermal oxidation of oleic acid investigated by combination of EPR spectroscopy and SPME-GC-MS/MS.

Science.gov (United States)

Chen, Hongjian; Cao, Peirang; Li, Bo; Sun, Dewei; Wang, Yong; Li, Jinwei; Liu, Yuanfa

2017-04-15

Promotion of water to the thermal oxidation of oleic acid was detected by the combination of EPR, SPME-GC-MS/MS and GC. Spin-trapping technique was used to identify and quantify the radical species formed during thermal oxidation of oleic acid by using DMPO as electron spin trap. The most abundant radical species were identified as DMPO-alkyl radical adducts. EPR intensity plateau of the samples with 5% water content was 140% higher than the samples without water. It implies oleic acid samples with high water content had high level of oxidation rates. The proportion of aldehydes of the samples with 2% water content was the maximum about 59.97%. Among the formed products, (E,E)-2,4-decadienal has genotoxic and cytotoxic effects, whose percentage was nearly twice comparing with that of 5-0% water content. This study demonstrated that higher water content in frying systems would contribute to seriously oxidation and degradation of oleic acids. Copyright © 2016 Elsevier Ltd. All rights reserved.

Analysis of volatile headspace gases sampled by cryogenic traps from Westinghouse Hanford Company Tank 242-C-112 March 1992

International Nuclear Information System (INIS)

Lucke, R.B.; Clauss, S.A.

1993-10-01

Results are given from gas chromatography/mass spectrometry (GC/MS) analyses of the headspace samples obtained by using cryogenic traps from Westinghouse Hanford Company (WHC) Tank 112-C during the month of March, 1992. Samples were analyzed as received with no sample preparation. Analyses included direct GC/MS for volatile/semivolatile components, and direct GC/MS for ammonia. Purge and trap GC/MS analysis was not done. In addition, aliquots were sent to Karl Pool, Pacific Northwest Laboratory, for hydrogen cyanide analysis by ion chromatography, the results are reported here. All concentrations are reported for the methanol extract solutions. To calculate concentrations in the headspace, the cryo-sampling air volume and the methanol rinse volume must be obtained from cryo-sampling personnel at WHC. Triplicate analyses were done on all samples, and average concentrations and standard deviations are reported. One significant result was that no ammonia was detected

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

Science.gov (United States)

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

2015-01-01

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.

GC ‘Multi-Analyte’ Detection Method

Energy Technology Data Exchange (ETDEWEB)

Dudar, E. [Plant Protection & Soil Conservation Service of Budapest, Budapest (Hungary)

2009-07-15

Elaborated methodologies for GC multi-analyte detection are presented, comprising the steps of method development, chromatographic conditions and procedures including the determination of relative retention times and summary results tables. (author)

Ambient mass spectrometry employing direct analysis in real time (DART) ion source for olive oil quality and authenticity assessment

International Nuclear Information System (INIS)

Vaclavik, Lukas; Cajka, Tomas; Hrbek, Vojtech; Hajslova, Jana

2009-01-01

A novel approach for the authentication of olive oil samples representing different quality grades has been developed. A new type of ion source, direct analysis in real time (DART), coupled to a high-resolution time-of-flight mass spectrometer (TOFMS) was employed for the comprehensive profiling of triacylglycerols (TAGs) and/or polar compounds extracted with a methanol-water mixture. The main parameters influencing the ionization efficiency of TAGs were the type of sample solvent, degree of sample dilution, ion beam temperature, and presence of a dopant (ammonia vapors). The ionization yield of polar compounds depended mainly on a content of water in the extract and ion beam temperature. Using DART-TOFMS, not only differentiation among extra virgin olive oil (EVOO), olive pomace oil (OPO) and olive oil (OO) could be easily achieved, but also EVOO adulteration with commonly used adulterant, hazelnut oil (HO), was feasible. Based on the linear discriminant analysis (LDA), the introduced method allowed detection of HO addition of 6 and 15% (v/v) when assessing DART-TOFMS mass profiles of polar compounds and TAGs, respectively.

Ambient mass spectrometry employing direct analysis in real time (DART) ion source for olive oil quality and authenticity assessment

Energy Technology Data Exchange (ETDEWEB)

Vaclavik, Lukas; Cajka, Tomas; Hrbek, Vojtech [Institute of Chemical Technology Prague, Faculty of Food and Biochemical Technology, Department of Food Chemistry and Analysis, Technicka 5, 166 28 Prague 6 (Czech Republic); Hajslova, Jana, E-mail: jana.hajslova@vscht.cz [Institute of Chemical Technology Prague, Faculty of Food and Biochemical Technology, Department of Food Chemistry and Analysis, Technicka 5, 166 28 Prague 6 (Czech Republic)

2009-07-10

A novel approach for the authentication of olive oil samples representing different quality grades has been developed. A new type of ion source, direct analysis in real time (DART), coupled to a high-resolution time-of-flight mass spectrometer (TOFMS) was employed for the comprehensive profiling of triacylglycerols (TAGs) and/or polar compounds extracted with a methanol-water mixture. The main parameters influencing the ionization efficiency of TAGs were the type of sample solvent, degree of sample dilution, ion beam temperature, and presence of a dopant (ammonia vapors). The ionization yield of polar compounds depended mainly on a content of water in the extract and ion beam temperature. Using DART-TOFMS, not only differentiation among extra virgin olive oil (EVOO), olive pomace oil (OPO) and olive oil (OO) could be easily achieved, but also EVOO adulteration with commonly used adulterant, hazelnut oil (HO), was feasible. Based on the linear discriminant analysis (LDA), the introduced method allowed detection of HO addition of 6 and 15% (v/v) when assessing DART-TOFMS mass profiles of polar compounds and TAGs, respectively.

Molecular cloning, homology modeling and site-directed mutagenesis of vanadium-dependent bromoperoxidase (GcVBPO1) from Gracilaria changii (Rhodophyta).

Science.gov (United States)

Baharum, H; Chu, W-C; Teo, S-S; Ng, K-Y; Rahim, R Abdul; Ho, C-L

2013-08-01

Vanadium-dependent haloperoxidases belong to a class of vanadium enzymes that may have potential industrial and pharmaceutical applications due to their high stability. In this study, the 5'-flanking genomic sequence and complete reading frame encoding vanadium-dependent bromoperoxidase (GcVBPO1) was cloned from the red seaweed, Fracilaria changii, and the recombinant protein was biochemically characterized. The deduced amino acid sequence of GcVBPO1 is 1818 nucleotides in length, sharing 49% identity with the vanadium-dependent bromoperoxidases from Corralina officinalis and Cor. pilulifera, respectively. The amino acid residues associated with the binding site of vanadate cofactor were found to be conserved. The Km value of recombinant GcVBPO1 for Br(-) was 4.69 mM, while its Vmax was 10.61 μkat mg(-1) at pH 7. Substitution of Arg(379) with His(379) in the recombinant protein caused a lower affinity for Br(-), while substitution of Arg(379) with Phe(379) not only increased its affinity for Br(-) but also enabled the mutant enzyme to oxidize Cl(-). The mutant Arg(379)Phe was also found to have a lower affinity for I(-), as compared to the wild-type GcVBPO1 and mutant Arg(379)His. In addition, the Arg(379)Phe mutant has a slightly higher affinity for H2O2 compared to the wild-type GcVBPO1. Multiple cis-acting regulatory elements associated with light response, hormone signaling, and meristem expression were detected at the 5'-flanking genomic sequence of GcVBPO1. The transcript abundance of GcVBPO1 was relatively higher in seaweed samples treated with 50 parts per thousand (ppt) artificial seawater (ASW) compared to those treated in 10 and 30 ppt ASW, in support of its role in the abiotic stress response of seaweed. Copyright © 2013 Elsevier Ltd. All rights reserved.

Tile-based Fisher-ratio software for improved feature selection analysis of comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry data.

Science.gov (United States)

Marney, Luke C; Siegler, W Christopher; Parsons, Brendon A; Hoggard, Jamin C; Wright, Bob W; Synovec, Robert E

2013-10-15

Comprehensive two-dimensional (2D) gas chromatography coupled with time-of-flight mass spectrometry (GC × GC-TOFMS) is a highly capable instrumental platform that produces complex and information-rich multi-dimensional chemical data. The data can be initially overwhelming, especially when many samples (of various sample classes) are analyzed with multiple injections for each sample. Thus, the data must be analyzed in such a way as to extract the most meaningful information. The pixel-based and peak table-based Fisher ratio algorithmic approaches have been used successfully in the past to reduce the multi-dimensional data down to those chemical compounds that are changing between the sample classes relative to those that are not changing (i.e., chemical feature selection). We report on the initial development of a computationally fast novel tile-based Fisher-ratio software that addresses the challenges due to 2D retention time misalignment without explicitly aligning the data, which is often a shortcoming for both pixel-based and peak table-based algorithmic approaches. Concurrently, the tile-based Fisher-ratio algorithm significantly improves the sensitivity contrast of true positives against a background of potential false positives and noise. In this study, eight compounds, plus one internal standard, were spiked into diesel at various concentrations. The tile-based F-ratio algorithmic approach was able to "discover" all spiked analytes, within the complex diesel sample matrix with thousands of potential false positives, in each possible concentration comparison, even at the lowest absolute spiked analyte concentration ratio of 1.06, the ratio between the concentrations in the spiked diesel sample to the native concentration in diesel. Copyright © 2013 Elsevier B.V. All rights reserved.

Ectopic expression of AID in a non-B cell line triggers A:T and G:C point mutations in non-replicating episomal vectors.

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Tihana Jovanic

Full Text Available Somatic hypermutation (SHM of immunoglobulin genes is currently viewed as a two step process initiated by the deamination of deoxycytidine (C to deoxyuridine (U, catalysed by the activation induced deaminase (AID. Phase 1 mutations arise from DNA replication across the uracil residue or the abasic site, generated by the uracil-DNA glycosylase, yielding transitions or transversions at G:C pairs. Phase 2 mutations result from the recognition of the U:G mismatch by the Msh2/Msh6 complex (MutS Homologue, followed by the excision of the mismatched nucleotide and the repair, by the low fidelity DNA polymerase eta, of the gap generated by the exonuclease I. These mutations are mainly focused at A:T pairs. Whereas in activated B cells both G:C and A:T pairs are equally targeted, ectopic expression of AID was shown to trigger only G:C mutations on a stably integrated reporter gene. Here we show that when using non-replicative episomal vectors containing a GFP gene, inactivated by the introduction of stop codons at various positions, a high level of EGFP positive cells was obtained after transient expression in Jurkat cells constitutively expressing AID. We show that mutations at G:C and A:T pairs are produced. EGFP positive cells are obtained in the absence of vector replication demonstrating that the mutations are dependent only on the mismatch repair (MMR pathway. This implies that the generation of phase 1 mutations is not a prerequisite for the expression of phase 2 mutations.

Organization of GC/MS and LC/MS metabolomics data into chemical libraries

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DeHaven Corey D

2010-10-01

Full Text Available Abstract Background Metabolomics experiments involve generating and comparing small molecule (metabolite profiles from complex mixture samples to identify those metabolites that are modulated in altered states (e.g., disease, drug treatment, toxin exposure. One non-targeted metabolomics approach attempts to identify and interrogate all small molecules in a sample using GC or LC separation followed by MS or MSn detection. Analysis of the resulting large, multifaceted data sets to rapidly and accurately identify the metabolites is a challenging task that relies on the availability of chemical libraries of metabolite spectral signatures. A method for analyzing spectrometry data to identify and Quantify Individual Components in a Sample, (QUICS, enables generation of chemical library entries from known standards and, importantly, from unknown metabolites present in experimental samples but without a corresponding library entry. This method accounts for all ions in a sample spectrum, performs library matches, and allows review of the data to quality check library entries. The QUICS method identifies ions related to any given metabolite by correlating ion data across the complete set of experimental samples, thus revealing subtle spectral trends that may not be evident when viewing individual samples and are likely to be indicative of the presence of one or more otherwise obscured metabolites. Results LC-MS/MS or GC-MS data from 33 liver samples were analyzed simultaneously which exploited the inherent biological diversity of the samples and the largely non-covariant chemical nature of the metabolites when viewed over multiple samples. Ions were partitioned by both retention time (RT and covariance which grouped ions from a single common underlying metabolite. This approach benefitted from using mass, time and intensity data in aggregate over the entire sample set to reject outliers and noise thereby producing higher quality chemical identities. The

Supercritical Fluid Chromatography- A Hybrid of GC and LC

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Kaushal K Chandrul

2010-03-01

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High performance specifications and unique functionality of chromatographic techniques is a demand of pharmaceutical industry and research. This leads to the origin of Supercritical Fluid Chromatography (SFC. It is a rapidly expanding analytical technique. The main feature that differentiates SFC from other chromatographic techniques is the replacement of either the liquid or gas mobile phase with a supercritical fluid mobile phase. It is considered a hybrid of GC and LC technique. High diffusion coefficient and low viscosity of supercritical fluids is responsible for high speed analysis, high efficiency and high sensitivity. Low mobile-phase flow rate, density programming and compatability with GC and LC detectors make SFC a versatile chromatographic technique in analytical research and development. It has a unique characteristic of analyzing thermo labile or non-volatile substances. This review highlights the role of supercritical fluid chromatography in the separation of polymers, thermally labile pesticides, fatty acids, metal chelates and organometallic compounds, chiral and achiral molecules, identification and analysis of polar samples, explosives, drugs of abuse and application of SFC in forensic science (fingerprinting. 

Development of the HS-SPME-GC-MS/MS method for analysis of chemical warfare agent and their degradation products in environmental samples.

Science.gov (United States)

Nawała, Jakub; Czupryński, Krzysztof; Popiel, Stanisław; Dziedzic, Daniel; Bełdowski, Jacek

2016-08-24

After World War II approximately 50,000 tons of chemical weapons were dumped in the Baltic Sea by the Soviet Union under the provisions of the Potsdam Conference on Disarmament. These dumped chemical warfare agents still possess a major threat to the marine environment and to human life. Therefore, continue monitoring of these munitions is essential. In this work, we present the application of new solid phase microextraction fibers in analysis of chemical warfare agents and their degradation products. It can be concluded that the best fiber for analysis of sulfur mustard and its degradation products is butyl acrylate (BA), whereas for analysis of organoarsenic compounds and chloroacetophenone, the best fiber is a co-polymer of methyl acrylate and methyl methacrylate (MA/MMA). In order to achieve the lowest LOD and LOQ the samples should be divided into two subsamples. One of them should be analyzed using a BA fiber, and the second one using a MA/MMA fiber. When the fast analysis is required, the microextraction should be performed by use of a butyl acrylate fiber because the extraction efficiency of organoarsenic compounds for this fiber is acceptable. Next, we have elaborated of the HS-SPME-GC-MS/MS method for analysis of CWA degradation products in environmental samples using laboratory obtained fibers The analytical method for analysis of organosulfur and organoarsenic compounds was optimized and validated. The LOD's for all target chemicals were between 0.03 and 0.65 ppb. Then, the analytical method developed by us, was used for the analysis of sediment and pore water samples from the Baltic Sea. During these studies, 80 samples were analyzed. It was found that 25 sediments and 5 pore water samples contained CWA degradation products such as 1,4-dithiane, 1,4-oxathiane or triphenylarsine, the latter being a component of arsine oil. The obtained data is evidence that the CWAs present in the Baltic Sea have leaked into the general marine environment. Copyright �

Use of a holder-vacuum tube device to save on-site hands in preparing urine samples for head-space gas-chromatography, and its application to determine the time allowance for sample sealing.

Science.gov (United States)

Kawai, Toshio; Sumino, Kimiaki; Ohashi, Fumiko; Ikeda, Masayuki

2011-01-01

To facilitate urine sample preparation prior to head-space gas-chromatographic (HS-GC) analysis. Urine samples containing one of the five solvents (acetone, methanol, methyl ethyl ketone, methyl isobutyl ketone and toluene) at the levels of biological exposure limits were aspirated into a vacuum tube via holder, a device commercially available for venous blood collection (the vacuum tube method). The urine sample, 5 ml, was quantitatively transferred to a 20-ml head-space vial prior to HS-GC analysis. The loaded tubes were stored at +4 ℃ in dark for up to 3 d. The vacuum tube method facilitated on-site procedures of urine sample preparation for HS-GC with no significant loss of solvents in the sample and no need of skilled hands, whereas on-site sample preparation time was significantly reduced. Furthermore, no loss of solvents was detected during the 3-d storage, irrespective of hydrophilic (acetone) or lipophilic solvent (toluene). In a pilot application, high performance of the vacuum tube method in sealing a sample in an air-tight space succeeded to confirm that no solvent will be lost when sealing is completed within 5 min after urine voiding, and that the allowance time is as long as 30 min in case of toluene in urine. The use of the holder-vacuum tube device not only saves hands for transfer of the sample to air-tight space, but facilitates sample storage prior to HS-GC analysis.

Drug testing data from the 2007 Pan American Games: delta13C values of urinary androsterone, etiocholanolone and androstanediols determined by GC/C/IRMS.

Science.gov (United States)

Aguilera, Rodrigo; Chapman, Thomas E; Pereira, Henrique; Oliveira, Giselle C; Illanes, Renata P; Fernandes, Telma F; Azevedo, Débora A; Neto, Francisco Aquino

2009-07-01

The main purpose of this article is to show the application of the CG/C/IRMS in real time during competition in the steroid confirmation analysis. For this reason, this paper summarizes the results obtained from the doping control analysis during the period of the 2007 Pan American Games held in Rio de Janeiro, Brazil. Approximately 5600 athletes from 42 different countries competed in the games. Testing was performed in accordance to World Anti-Doping Agency (WADA) technical note for prohibited substances. This paper reports data where abnormal urinary steroid profiles, have been found with the screening procedures. One 8 mL urine sample was used for the analysis of five steroid metabolites with two separate analyses by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Urine samples were submitted to GC/C/IRMS for confirmation analysis to determine the (13)C/(12)C ratio of selected steroids. Fifty-seven urine samples were analyzed by GC/C/IRMS and the delta(13)C values ( per thousand) of androsterone, etiocholanolone, 5beta-androstane-3alpha, 17beta-diol (5beta-diol), 5alpha-androstane-3alpha, 17beta-diol (5alpha-diol) and 5beta-pregnane-3alpha, 20alpha-diol (5beta-pdiol), the endogenous reference compound are presented. One urine sample with a testosterone/epitestosterone (T/E) ratio of 4.7 was confirmed to be positive of doping by GC/C/IRMS analysis. The delta values of 5beta-diol and 5alpha-diol were 3.8 and 10.8, respectively, compared to the endogenous reference compound 5beta-pdiol, which exceeded the WADA limit of 3 per thousand. The results obtained by CG/C/IRMS confirmation analyses, in suspicious samples, were conclusive in deciding whether or not a doping steroid violation had occurred.

Analysis of Endocrine Disrupting Pesticides by Capillary GC with Mass Spectrometric Detection

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Svetlana Hrouzková

2012-09-01

Full Text Available Endocrine disrupting chemicals, among them many pesticides, alter the normal functioning of the endocrine system of both wildlife and humans at very low concentration levels. Therefore, the importance of method development for their analysis in food and the environment is increasing. This also covers contributions in the field of ultra-trace analysis of multicomponent mixtures of organic pollutants in complex matrices. With this fact conventional capillary gas chromatography (CGC and fast CGC with mass spectrometric detection (MS has acquired a real importance in the analysis of endocrine disrupting pesticide (EDP residues. This paper provides an overview of GC methods, including sample preparation steps, for analysis of EDPs in a variety of matrices at ultra-trace concentration levels. Emphasis is put on separation method, mode of MS detection and ionization and obtained limits of detection and quantification. Analysis time is one of the most important aspects that should be considered in the choice of analytical methods for routine analysis. Therefore, the benefits of developed fast GC methods are important.

Combination of capillary GC, GC/MS and 13C-NMR for the characterization of the rhizome oil of Piper betle L. (Piperaceae) from Vietnam

NARCIS (Netherlands)

Thanh, L.; Dung, N.X.; Bighelli, A.; Casanova, J.; Leclercq, P.A.

1997-01-01

The essential oil from the rhizomes of Piper betle L. (betel), collected around Hue, was obtained in 0.20% yield. The oil was examined by a combination of capillary GC and GC/MS. 13C-NMR studies confirmed the structure assignments proposed by retention data and mass spectra of the components with a

A simple model for the influence of meiotic conversion tracts on GC content.

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Marie-Claude Marsolier-Kergoat

Full Text Available A strong correlation between GC content and recombination rate is observed in many eukaryotes, which is thought to be due to conversion events linked to the repair of meiotic double-strand breaks. In several organisms, the length of conversion tracts has been shown to decrease exponentially with increasing distance from the sites of meiotic double-strand breaks. I show here that this behavior leads to a simple analytical model for the evolution and the equilibrium state of the GC content of sequences devoid of meiotic double-strand break sites. In the yeast Saccharomyces cerevisiae, meiotic double-strand breaks are practically excluded from protein-coding sequences. A good fit was observed between the predictions of the model and the variations of the average GC content of the third codon position (GC3 of S. cerevisiae genes. Moreover, recombination parameters that can be extracted by fitting the data to the model coincide with experimentally determined values. These results thus indicate that meiotic recombination plays an important part in determining the fluctuations of GC content in yeast coding sequences. The model also accounted for the different patterns of GC variations observed in the genes of Candida species that exhibit a variety of sexual lifestyles, and hence a wide range of meiotic recombination rates. Finally, the variations of the average GC3 content of human and chicken coding sequences could also be fitted by the model. These results suggest the existence of a widespread pattern of GC variation in eukaryotic genes due to meiotic recombination, which would imply the generality of two features of meiotic recombination: its association with GC-biased gene conversion and the quasi-exclusion of meiotic double-strand breaks from coding sequences. Moreover, the model points out to specific constraints on protein fragments encoded by exon terminal sequences, which are the most affected by the GC bias.

Automated GC-MS analysis of free amino acids in biological fluids.

Science.gov (United States)

Kaspar, Hannelore; Dettmer, Katja; Gronwald, Wolfram; Oefner, Peter J

2008-07-15

A gas chromatography-mass spectrometry (GC-MS) method was developed for the quantitative analysis of free amino acids as their propyl chloroformate derivatives in biological fluids. Derivatization with propyl chloroformate is carried out directly in the biological samples without prior protein precipitation or solid-phase extraction of the amino acids, thereby allowing automation of the entire procedure, including addition of reagents, extraction and injection into the GC-MS. The total analysis time was 30 min and 30 amino acids could be reliably quantified using 19 stable isotope-labeled amino acids as internal standards. Limits of detection (LOD) and lower limits of quantification (LLOQ) were in the range of 0.03-12 microM and 0.3-30 microM, respectively. The method was validated using a certified amino acid standard and reference plasma, and its applicability to different biological fluids was shown. Intra-day precision for the analysis of human urine, blood plasma, and cell culture medium was 2.0-8.8%, 0.9-8.3%, and 2.0-14.3%, respectively, while the inter-day precision for human urine was 1.5-14.1%.

GC/FID-based authentication of Baccharis trimera: a quality control study of products commercialized in Curitiba and metropolitan region (Brazil

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Lia M. S. de Ferrante

Full Text Available Baccharis trimera (carqueja is a medicinal plant used for stomach pain, bad digestion, heart bum, kidney problems and constipation. The objective of the present work was a quality study of carqueja commercialized in Curitiba and metropolitan region (Paraná-Brazil using gas chromatography techniques (GC/FID for analyses of the essential oil, which was extracted through hydrodistillation using a Clevenger system. Macro and microscopic analyses were also done. Some samples were contaminated by other species of plants, fungi and small insects, some of them could be identified. Among all samples, 21 showed similar chromatographic profile to the standard oil, and 7 had different profile in relation to the standard. The chromatogram analyses showed that most of the analyzed samples had the similar profile as the standard oil of Baccharis trimera. GC/FID-based authentication of Baccharis trimera may be useful as a rapid tool to ensure quality control and safety monitoring of this kind of herbal pharmaceuticals.

A novel chiral GC/MS method for the analysis of fluoxetine and norfluoxetine enantiomers in biological fluids

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Janet Mifsud

2012-01-01

Full Text Available Aims: A novel robust chiral gas chromatographic/mass spectrometric (GC/MS method for the separation and measurement of fluoxetine and norfluoxetine enantiomers in urine and plasma was developed. Materials and Methods: The drug was extracted from the samples by a liquid-liquid technique, using chloroform, and the enantiomers were separated and measured on a chiral gas chromatographic column (HYDRODEX β-6TBDM®, 0.25 μm × 0.25 mm × 50 m. GC/MS instrumentation was used for the acquisition of data in the electron impact selective-ion monitoring mode. Results: The ions chosen were of a mass-to-charge ratio (m/z exactly equal to 44 units, in order to measure fluoxetine enantiomers, 134 units in order to measure norfluoxetine enantiomers, and 58 units in order to measure diphenhydramine, the internal standard. The method was found to be linear and reproducible in the 50-500 ng/mL concentration range for both urine samples and plasma samples and for both fluoxetine and norfluoxetine, with correlation coefficients ranging between 0.994 and 0.997. Conclusions: This methodology has an enormous potential for application in pharmacokinetic studies of the enantiomers of fluoxetine

Both selective and neutral processes drive GC content evolution in the human genome

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Cagliani Rachele

2008-03-01

Full Text Available Abstract Background Mammalian genomes consist of regions differing in GC content, referred to as isochores or GC-content domains. The scientific debate is still open as to whether such compositional heterogeneity is a selected or neutral trait. Results Here we analyze SNP allele frequencies, retrotransposon insertion polymorphisms (RIPs, as well as fixed substitutions accumulated in the human lineage since its divergence from chimpanzee to indicate that biased gene conversion (BGC has been playing a role in within-genome GC content variation. Yet, a distinct contribution to GC content evolution is accounted for by a selective process. Accordingly, we searched for independent evidences that GC content distribution does not conform to neutral expectations. Indeed, after correcting for possible biases, we show that intron GC content and size display isochore-specific correlations. Conclusion We consider that the more parsimonious explanation for our results is that GC content is subjected to the action of both weak selection and BGC in the human genome with features such as nucleosome positioning or chromatin conformation possibly representing the final target of selective processes. This view might reconcile previous contrasting findings and add some theoretical background to recent evidences suggesting that GC content domains display different behaviors with respect to highly regulated biological processes such as developmentally-stage related gene expression and programmed replication timing during neural stem cell differentiation.

Antitumor effect of degalactosylated gc-globulin on orthotopic grafted lung cancer in mice.

Science.gov (United States)

Hirota, Keiji; Nakagawa, Yoshinori; Takeuchi, Ryota; Uto, Yoshihiro; Hori, Hitoshi; Onizuka, Shinya; Terada, Hiroshi

2013-07-01

Group-specific component (Gc)-globulin-derived macrophage-activating factor (GcMAF) generated by a cascade of catalytic reactions with deglycosidase enzymes exerts antitumor activity. We hypothesized that degalactosyl Gc-globulin (DG3), a precursor of GcMAF, also plays a role in recovery from cancer as well as GcMAF due to progression of deglycosylation by generally resident sialidases and mannosidases. We prepared the subtypes of DG3, such as 1f1f and 1s1s and its 22 homodimers, by using vitamin D3-binding Sepharose CL-6B and examined their antitumor activity in mice bearing Lewis lung carcinoma cells, by counting the number of nodules formed in their lungs. Antitumor activity of DG3 was observed regardless of its subtype, being equivalent to that of GcMAF. The injection route of DG3 affected its antitumor activity, with subcutaneous and intramuscular administration being more favorable than the intraperitoneal or intravenous route. In order to obtain significant antitumor activity, more than 160 ng/kg of DG3 were required. DG3 proved to be promising as an antitumor agent, similarly to GcMAF.

Synthesis and Enhanced Ethanol Gas Sensing Properties of the g-C3N4 Nanosheets-Decorated Tin Oxide Flower-Like Nanorods Composite

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Yan Wang

2017-09-01

Full Text Available Flower-like SnO2/g-C3N4 nanocomposites were synthesized via a facile hydrothermal method by using SnCl4·5H2O and urea as the precursor. The structure and morphology of the as-synthesized samples were characterized by using the X-ray powder diffraction (XRD, electron microscopy (FESEM and TEM, and Fourier transform infrared spectrometer (FT-IR techniques. SnO2 displays the unique 3D flower-like microstructure assembled with many uniform nanorods with the lengths and diameters of about 400–600 nm and 50–100 nm, respectively. For the SnO2/g-C3N4 composites, SnO2 flower-like nanorods were coupled by a lamellar structure 2D g-C3N4. Gas sensing performance test results indicated that the response of the sensor based on 7 wt. % 2D g-C3N4-decorated SnO2 composite to 500 ppm ethanol vapor was 150 at 340 °C, which was 3.5 times higher than that of the pure flower-like SnO2 nanorods-based sensor. The gas sensing mechanism of the g-C3N4nanosheets-decorated SnO2 flower-like nanorods was discussed in relation to the heterojunction structure between g-C3N4 and SnO2.

Effects of vitamin D(3)-binding protein-derived macrophage activating factor (GcMAF) on angiogenesis.

Science.gov (United States)

Kanda, Shigeru; Mochizuki, Yasushi; Miyata, Yasuyoshi; Kanetake, Hiroshi; Yamamoto, Nobuto

2002-09-04

The vitamin D(3)-binding protein (Gc protein)-derived macrophage activating factor (GcMAF) activates tumoricidal macrophages against a variety of cancers indiscriminately. We investigated whether GcMAF also acts as an antiangiogenic factor on endothelial cells. The effects of GcMAF on angiogenic growth factor-induced cell proliferation, chemotaxis, and tube formation were examined in vitro by using cultured endothelial cells (murine IBE cells, porcine PAE cells, and human umbilical vein endothelial cells [HUVECs]) and in vivo by using a mouse cornea micropocket assay. Blocking monoclonal antibodies to CD36, a receptor for the antiangiogenic factor thrombospondin-1, which is also a possible receptor for GcMAF, were used to investigate the mechanism of GcMAF action. GcMAF inhibited the endothelial cell proliferation, chemotaxis, and tube formation that were all stimulated by fibroblast growth factor-2 (FGF-2), vascular endothelial growth factor-A, or angiopoietin 2. FGF-2-induced neovascularization in murine cornea was also inhibited by GcMAF. Monoclonal antibodies against murine and human CD36 receptor blocked the antiangiogenic action of GcMAF on the angiogenic factor stimulation of endothelial cell chemotaxis. In addition to its ability to activate tumoricidal macrophages, GcMAF has direct antiangiogenic effects on endothelial cells independent of tissue origin. The antiangiogenic effects of GcMAF may be mediated through the CD36 receptor.

Environmental trace analysis by means of supersensitive GC-IMS

International Nuclear Information System (INIS)

Leonhardt, J.W.

1997-01-01

The effective control of pollutants in ambient air requires their fast in situ identification and concentration determination of chemical compounds in the range of micrograms per m 3 . There are attempts to use conventional analytical techniques as portable GC and GC-MS. These systems are relatively expensive. A new supersensitive ion Mobility Sensor (IMS) was developed and checked by IUT Ltd, which meets the new demands. The use of tritium sources is an advantage in comparison with other IMS being equipped by nickel-63, the application of which is rather critical in respect of the radiation protection. On the other hand an integrated separation column allows to reduce interferences by matrix effects. The technical parameters of the IUT GC- IMS and some of its most important applications are briefly presented

SOLID PHASE MICRO EXTRACTION (SPME) FLAVOR ANALYSIS OF APPLE JUICE AND COFFEE MIXTURES USING GAS CHROMATOGRAPHY-MASS SPECTROMETRY (GC-MS)

OpenAIRE

Mi Ja Kim; Jeehyun Lee; Jaeyoung Byun; Sunmi Choi; Wonsik Choi

2016-01-01

This research was conducted to evaluate the flavor of apple juice and coffee mixtures and the sensory quality of SPME extracts using gas chromatography-mass spectrometry (GC-MS). Three samples with different compositions were examined. Sample A1 contained85% apple juiceand 15% coffee, sample A2 had87.5% apple and 12.5% coffee, and sample A3 had90% apple juiceand 10% coffee. The sensory analysis involved 100 panelists and a sequential monadic test. Sample presentation orders were balanced in ...

Determination of carbohydrates in medicinal plants--comparison between TLC, mf-MELDI-MS and GC-MS.

Science.gov (United States)

Qureshi, Muhammad Nasimullah; Stecher, Guenther; Sultana, Tahira; Abel, Gudrun; Popp, Michael; Bonn, Guenther K

2011-01-01

Quality control in the pharmaceutical and phytopharmaceutical industries requires fast and reliable methods for the analysis of raw materials and final products. This study evaluates different analytical approaches in order to recognise the most suitable technique for the analysis of carbohydrates in herbal drug preparations. The specific focus of the study is on thin-layer chromatography (TLC), gas chromatography (GC), and a newly developed mass spectrometric method, i.e. matrix free material enhanced laser desorption/ionisation time of flight mass spectrometry (mf-MELDI-MS). Samples employed in the study were standards and microwave-assisted water extracts from Quercus. TLC analysis proved the presence of mono-, di- and trisaccharides within the biological sample and hinted at the existence of an unknown carbohydrate of higher oligomerisation degree. After evaluation of different derivatisation techniques, GC-MS confirmed data obtained via TLC for mono- to trisaccharides, delivering additionally quantified values under a considerable amount of time. A carbohydrate of higher oligomerisation degree could not be found. The application of mf-MELDI-MS further confirmed the presence of carbohydrates up to trisaccharides, also hinting at the presence of a form of tetrasaccharide. Besides this information, mf-MELDI-MS delivered further data about other substances present in the extract. Quantitative determination resulted in 1.750, 1.736 and 0.336 mg/mL for glucose, sucrose and raffinose respectively. Evaluation of all three techniques employed, clearly proved the heightened performance of mf-MELDI-MS for the qualitative analysis of complex mixtures, as targets do not need modification and analysis requires only a few minutes. In addition, GC-MS is suitable for quantitative analysis. Copyright © 2011 John Wiley & Sons, Ltd.

Volatile-Compound Fingerprinting by Headspace-Gas-Chromatography Ion-Mobility Spectrometry (HS-GC-IMS) as a Benchtop Alternative to 1H NMR Profiling for Assessment of the Authenticity of Honey.

Science.gov (United States)

Gerhardt, Natalie; Birkenmeier, Markus; Schwolow, Sebastian; Rohn, Sascha; Weller, Philipp

2018-02-06

This work describes a simple approach for the untargeted profiling of volatile compounds for the authentication of the botanical origins of honey based on resolution-optimized HS-GC-IMS combined with optimized chemometric techniques, namely PCA, LDA, and kNN. A direct comparison of the PCA-LDA models between the HS-GC-IMS and 1 H NMR data demonstrated that HS-GC-IMS profiling could be used as a complementary tool to NMR-based profiling of honey samples. Whereas NMR profiling still requires comparatively precise sample preparation, pH adjustment in particular, HS-GC-IMS fingerprinting may be considered an alternative approach for a truly fully automatable, cost-efficient, and in particular highly sensitive method. It was demonstrated that all tested honey samples could be distinguished on the basis of their botanical origins. Loading plots revealed the volatile compounds responsible for the differences among the monofloral honeys. The HS-GC-IMS-based PCA-LDA model was composed of two linear functions of discrimination and 10 selected PCs that discriminated canola, acacia, and honeydew honeys with a predictive accuracy of 98.6%. Application of the LDA model to an external test set of 10 authentic honeys clearly proved the high predictive ability of the model by correctly classifying them into three variety groups with 100% correct classifications. The constructed model presents a simple and efficient method of analysis and may serve as a basis for the authentication of other food types.

1000 human genomes carry widespread signatures of GC biased gene conversion.

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Dutta, Rajib; Saha-Mandal, Arnab; Cheng, Xi; Qiu, Shuhao; Serpen, Jasmine; Fedorova, Larisa; Fedorov, Alexei

2018-04-16

GC-Biased Gene Conversion (gBGC) is one of the important theories put forward to explain profound long-range non-randomness in nucleotide compositions along mammalian chromosomes. Nucleotide changes due to gBGC are hard to distinguish from regular mutations. Here, we present an algorithm for analysis of millions of known SNPs that detects a subset of so-called "SNP flip-over" events representing recent gBGC nucleotide changes, which occurred in previous generations via non-crossover meiotic recombination. This algorithm has been applied in a large-scale analysis of 1092 sequenced human genomes. Altogether, 56,328 regions on all autosomes have been examined, which revealed 223,955 putative gBGC cases leading to SNP flip-overs. We detected a strong bias (11.7% ± 0.2% excess) in AT- > GC over GC- > AT base pair changes within the entire set of putative gBGC cases. On average, a human gamete acquires 7 SNP flip-over events, in which one allele is replaced by its complementary allele during the process of meiotic non-crossover recombination. In each meiosis event, on average, gBGC results in replacement of 7 AT base pairs by GC base pairs, while only 6 GC pairs are replaced by AT pairs. Therefore, every human gamete is enriched by one GC pair. Happening over millions of years of evolution, this bias may be a noticeable force in changing the nucleotide composition landscape along chromosomes.

Reference standards for quantitative trace analysis of PCB's by GC. Technical PCB formulations for the calibration of ECD and MSD responses

Energy Technology Data Exchange (ETDEWEB)

Krupcik, J. (Slovak Technical Univ., Department of Analytical Chemistry, Bratislava (Slovakia)); Kocan, A. (Institute of Preventive Medicine, Bratislava (Slovakia)); Petrik, J. (Institute of Preventive Medicine, Bratislava (Slovakia)); Leclercq, P.A. (Eindhoven University of Technology, Dept. of Chemical Engineering, Lab. of Instrumental Analysis (Netherlands)); Ballschmiter, K. (University of Ulm, Dept. of Analytical and Environmental Chemistry (Germany))

1993-04-01

The composition of any technical PCB formulation can be determined directly by analyzing the PCB sample by gas chromatography with a flame ionization detector (GC-FID), provided the relative molecular masses of the components are known. The response of electron capture and selected-ion monitoring, mass-spectra detectors can then be calibrated for individual PCB congeners by correlation of the chromatographic patterns with those of concentrated PCB samples obtained by GC-FID. This procedure, which uses a given technical PCB formulation as a secondary reference standard mixture, is to be preferred over existing calibration methods, when results with [+-]10% errors are acceptable because commercial PCB formulations cover the whole range of chlorination products. (orig.)

Rapid molecular screening of black carbon (biochar) thermosequences obtained from chestnut wood and rice straw: A pyrolysis-GC/MS study

International Nuclear Information System (INIS)

Kaal, Joeri; Schneider, Maximilian P.W.; Schmidt, Michael W.I.

2012-01-01

Rice straw and chestnut wood were heated between 200 and 1000 °C (T CHAR ) to produce Black C ‘thermosequences’. The molecular properties of the charred residues were assessed by pyrolysis-GC/MS to investigate the relation between charring intensity and pyrolysis fingerprint. Samples obtained at T CHAR > 500 °C (wood) or >700 °C (straw) gave low quality pyrograms and poor reproducibility because of high thermal stability, but pyrolysis-GC/MS allowed to track the thermal degradation of the main biocomponents (polysaccharides, lignin, methylene chain-based aliphatics, triterpenoids, chlorophyll and proteins) in the lower temperature range, mostly occurring between T CHAR 250 and 500 °C. With increasing T CHAR , the charred residues of these biocomponents lose characteristic functional groups, aromatise and finally condense into non-pyrolysable biomass. The proportions of the pyrolysis products of unspecific origin (benzene, toluene, PAHs, etc.), increase with charring intensity, while the ratios that reflect the abundance of alkyl cross-linkages between aromatic moieties (e.g. benzene/toluene, naphthalene/alkylnaphthalene) decrease. These results provide the guidelines to using pyrolysis-GC/MS for the molecular characterisation of different components in Black C and biochar, which is an important parameter for predicting Black C/biochar behaviour in soil. Results are consistent with earlier studies of these samples using the BPCA (benzenepolycarboxylic acid) method and the ring current-induced 13 C benzene chemical shift NMR (Nuclear Magnetic Resonance) approach. Pyrolysis-GC/MS provides more information on molecular structures in the low temperature range (T CHAR ≤ 500 °C) while the BPCA and NMR ring current methods provide more reliable estimations of charring intensity, especially at higher temperatures (T CHAR ≥ 500 °C). -- Highlights: ► Charred rice straw and chestnut wood (200–1000 °C) analysed by pyrolysis-GC/MS. ► Pyrolysis-GC/MS allows

A facile one-pot preparation of Co3O4/g-C3N4 heterojunctions with excellent electrocatalytic activity for the detection of environmental phenolic hormones

Science.gov (United States)

Sun, Yanjuan; Jiang, Jizhou; Liu, Yi; Wu, Shengli; Zou, Jing

2018-02-01

The Co3O4/g-C3N4 heterojunctions were prepared by a facile one-pot thermal decomposition technique. Compared with g-C3N4, it was found that Co3O4/g-C3N4 heterojunctions possessed a higher Brunner-Emmet-Teller (BET) surface area, which was beneficial to the diffusion of aim molecules on the electrode surfaces. And the optimal Co3O4/g-C3N4 heterojunctions exhibited a narrower band gap and a higher donor density, resulting in an excellent electrocatalytic activity for environmental phenolic hormones. Moreover, the Co3O4/g-C3N4 heterojunctions were used for the electrochemical sensing of environmental phenolic hormones such as bisphenol A, pentachlorophenol, p-nitrophenol and octylphenol. All detection ranges reached three orders of magnitude, showing a lower limit of detection of 10-9 mol L-1. So, sensitivity and accurate determination of environmental phenolic hormones in real water samples may use this Co3O4/g-C3N4 heterojunctions modified electrode.

Enhanced photocatalytic ozonation of organics by g-C3N4 under visible light irradiation

International Nuclear Information System (INIS)

Liao, Gaozu; Zhu, Dongyun; Li, Laisheng; Lan, Bingyan

2014-01-01

Highlights: • g-C 3 N 4 is employed as active catalyst in the photocatalytic ozonation system. • The more negative conduction band of g-C 3 N 4 benefits the transfer of electrons. • The synergistic effect between photocatalysis and ozonation is promoted by g-C 3 N 4 . • Enhanced degradation of oxalic acid and biphenol A is achieved via g-C 3 N 4 /Vis/O 3 . - Abstract: Graphitic carbon nitride (g-C 3 N 4 ) was employed as the active photocatalyst in the photocatalytic ozonation coupling system in the present study. g-C 3 N 4 was prepared by directly heating thiourea in air at 550 °C. XRD, FT-IR, UV–vis was used to characterize the structure and optical property. Oxalic acid and bisphenol A were selected as model substances for photocatalytic ozonation reactions to evaluate the catalytic ability of g-C 3 N 4 (g-C 3 N 4 /Vis/O 3 ). The results showed that the degradation ratio of oxalic acid with g-C 3 N 4 /Vis/O 3 was 65.2% higher than the sum of ratio when it was individually decomposed by g-C 3 N 4 /Vis and O 3 . The TOC removal of biphenol A with g-C 3 N 4 /Vis/O 3 was 2.17 times as great as the sum of the ratio when using g-C 3 N 4 /Vis and O 3 . This improvement was attributed to the enhanced synergistic effect between photocatalysis and ozonation by g-C 3 N 4 . Under visible light irradiation, the photo-generated electrons produced on g-C 3 N 4 facilitated the electrons transfer owing to the more negative conduction band potential (−1.3 V versus NHE). It meant that the photo-generated electrons could be trapped by ozone and reaction with it more easily. Subsequently, the yield of hydroxyl radicals was improved so as to enhance the organics degradation efficiency. This work indicated that metal-free g-C 3 N 4 could be an excellent catalyst for mineralization of organic compounds in waste control

Statistical model for classifying the feeding systems of Iberian pigs through Gas Chromatography (GC-FID and Isotope Ratio Mass Spectrometry (GC-C-IRMS

Directory of Open Access Journals (Sweden)

García-Casco, J. M.

2013-04-01

Full Text Available In the present work we have analyzed a total of 734 subcutaneous fat samples from Iberian pigs with different feeding systems for fattening (“Bellota”, “Recebo”, “Campo” and “Cebo” over three consecutive years, 2009-2011. Lipids were extracted from the subcutaneous fat on the rump, and after esterification, they were analyzed by Gas Chromatography (GC-FID and Gas Chromatography- Combustion-Isotope Ratio Mass Spectrometry (GC-C-IRMS. Mean fatty acids and isotope ratios show that there are differences according to the year and feeding systems, two factors that should be taken into account when classifying the animals. The application of different prediction models based on Discriminant analysis has allowed us to establish a method for the classification of animals according to the feeding system type, with a correct percentage of 85% using three or four classification categories (Bellota, Recebo, Campo and/or Cebo and 91% using only two categories, Cebo and Bellota. This model could provide the basis for appropriate classification of Iberian pigs according to their feeding regime.En el presente trabajo se han analizado un total de 734 muestras de tejido subcutáneo de cerdos ibéricos con distintos tipos de alimentación de engorde (Bellota, Recebo, Cebo y Campo a lo largo de tres años consecutivos, 2009-2011. Se han extraído los lípidos de la grasa subcutánea de rabadilla, y después de su esterificación, se han analizado por Cromatografía de gases (GC-FID y por Espectrometría de masas de relaciones isotópicas (GC-C-IRMS. Las medias de los ácidos grasos y de las relaciones isotópicas muestran que existen diferencias según el año y tipo de alimentación, factores que deberían tenerse en cuenta a la hora de clasificar los animales. La aplicación de distintos modelos de predicción basados en análisis discriminante permite establecer un método para la clasificación de los animales según el tipo de alimentación, con

Environmental trace analysis by means of supersensitive GC-IMS

Energy Technology Data Exchange (ETDEWEB)

Leonhardt, J.W. [IUTLimited, Berlin, (Germany)

1997-10-01

The effective control of pollutants in ambient air requires their fast in situ identification and concentration determination of chemical compounds in the range of micrograms per m{sup 3}. There are attempts to use conventional analytical techniques as portable GC and GC-MS. These systems are relatively expensive. A new supersensitive ion Mobility Sensor (IMS) was developed and checked by IUT Ltd, which meets the new demands. The use of tritium sources is an advantage in comparison with other IMS being equipped by nickel-63, the application of which is rather critical in respect of the radiation protection. On the other hand an integrated separation column allows to reduce interferences by matrix effects. The technical parameters of the IUT GC- IMS and some of its most important applications are briefly presented 6 refs., 1 tab., 5 figs.

PtNi Alloy Cocatalyst Modification of Eosin Y-Sensitized g-C3N4/GO Hybrid for Efficient Visible-Light Photocatalytic Hydrogen Evolution

Science.gov (United States)

Wang, Peng; Zong, Lanlan; Guan, Zhongjie; Li, Qiuye; Yang, Jianjun

2018-02-01

An economic and effective Pt-based alloy cocatalyst has attracted considerable attention due to their excellent catalytic activity and reducing Pt usage. In this study, PtNi alloy cocatalyst was successfully decorated on the g-C3N4/GO hybrid photocatalyst via a facile chemical reduction method. The Eosin Y-sensitized g-C3N4/PtNi/GO-0.5% composite photocatalyst yields about 1.54 and 1178 times higher hydrogen evolution rate than the Eosin Y-sensitized g-C3N4/Pt/GO-0.5% and g-C3N4/Ni/GO-0.5% samples, respectively. Mechanism of enhanced performance for the g-C3N4/PtNi/GO composite was also investigated by different characterization, such as photoluminescence, transient photocurrent response, and TEM. These results indicated that enhanced charge separation efficiency and more reactive sites are responsible for the improved hydrogen evolution performance due to the positive synergetic effect between Pt and Ni. This study suggests that PtNi alloy can be used as an economic and effective cocatalyst for hydrogen evolution reaction. [Figure not available: see fulltext.

GC content around splice sites affects splicing through pre-mRNA secondary structures

Directory of Open Access Journals (Sweden)

Chen Liang

2011-01-01

Full Text Available Abstract Background Alternative splicing increases protein diversity by generating multiple transcript isoforms from a single gene through different combinations of exons or through different selections of splice sites. It has been reported that RNA secondary structures are involved in alternative splicing. Here we perform a genomic study of RNA secondary structures around splice sites in humans (Homo sapiens, mice (Mus musculus, fruit flies (Drosophila melanogaster, and nematodes (Caenorhabditis elegans to further investigate this phenomenon. Results We observe that GC content around splice sites is closely associated with the splice site usage in multiple species. RNA secondary structure is the possible explanation, because the structural stability difference among alternative splice sites, constitutive splice sites, and skipped splice sites can be explained by the GC content difference. Alternative splice sites tend to be GC-enriched and exhibit more stable RNA secondary structures in all of the considered species. In humans and mice, splice sites of first exons and long exons tend to be GC-enriched and hence form more stable structures, indicating the special role of RNA secondary structures in promoter proximal splicing events and the splicing of long exons. In addition, GC-enriched exon-intron junctions tend to be overrepresented in tissue-specific alternative splice sites, indicating the functional consequence of the GC effect. Compared with regions far from splice sites and decoy splice sites, real splice sites are GC-enriched. We also found that the GC-content effect is much stronger than the nucleotide-order effect to form stable secondary structures. Conclusion All of these results indicate that GC content is related to splice site usage and it may mediate the splicing process through RNA secondary structures.

Detection of drugs in 275 alcohol-positive blood samples of Korean drivers.

Science.gov (United States)

Kim, Eunmi; Choe, Sanggil; Lee, Juseon; Jang, Moonhee; Choi, Hyeyoung; Chung, Heesun

2016-08-01

Since driving under the influence of drugs (DUID) is as dangerous as drink-driving, many countries regulate DUID by law. However, laws against the use of drugs while driving are not yet established in Korea. In order to investigate the type and frequency of drugs used by drivers in Korea, we analyzed controlled and non-controlled drugs in alcohol-positive blood samples. Total 275 blood samples were taken from Korean drivers, which were positive in roadside alcohol testing. The following analyses were performed: blood alcohol concentrations by GC; screening for controlled drugs by immunoassay and confirmation for positive samples by GC-MS. For the detection of DUID related drugs in blood samples, a total of 49 drugs were selected and were examined by GC-MS. For a rapid detection of these drugs, an automated identification software called "DrugMan" was used. Concentrations of alcohol in 275 blood samples ranged from 0.011 to 0.249% (average 0.119%). Six specimens showed positive results by immunoassay: one methamphetamine and five benzodiazepines I. By GC-MS confirmation, only benzodiazepines in four cases were identified, while methamphetamine and benzodiazepine in two cases were not detected from the presumptive positive blood samples. Using DrugMan, four drugs were detected; chlorpheniramine (5)*, diazepam (4), dextromethorphan (1) and doxylamine (1). In addition, ibuprofen (1), lidocaine (1) and topiramate (1) were also detected as general drugs in blood samples ('*' indicates frequency). The frequency of drug abuse by Korean drivers was relatively low and a total 14 cases were positive in 275 blood samples with a ratio of 5%. However it is necessary to analyze more samples including alcohol negative blood, and to expand the range of drug lists to get the detailed information. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

GC-C-IRMS in routine doping control practice: 3 years of drug testing data, quality control and evolution of the method.

Science.gov (United States)

Polet, Michael; Van Eenoo, Peter

2015-06-01

In order to detect the misuse of endogenous anabolic steroids, doping control laboratories require methods that allow differentiation between endogenous steroids and their synthetic copies. Gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS) is capable of measuring the carbon isotope ratio of urinary steroids and this allows differentiation between both. GC-C-IRMS and its application to doping control has evolved a lot during the last decade and so have the World Anti-Doping Agency (WADA) technical documents that describe how GC-C-IRMS should be applied. Especially the WADA technical document of 2014 introduced a number of obligatory quality controls and a fixed methodology that should be used by all the doping control laboratories. This document imposed more uniform methods between the laboratories in order to decrease the interlaboratory standard deviation and acquire similar results for the analysis of the same urine samples. In this paper, 3 years of drug testing data of our GC-C-IRMS method in routine doping control practice is described, with an emphasis on the new WADA technical document and its implementation. Useful data for other doping control laboratories is presented focussing on general method setup, quality control and data collected from routine samples. The paper concentrates on how IRMS results shift or remain similar by switching to the 2014 WADA technical document and gives insight in a straightforward approach to calculate the measurement uncertainty.

Determination of post-culture processing with carbohydrates by MALDI-MS and TMS derivatization GC-MS.

Science.gov (United States)

Wunschel, David S; Wahl, Karen L; Melville, Angela M; Sorensen, Christina M; Colburn, Heather A; Valentine, Nancy B; Stamper, Casey L

2011-10-15

Biological materials generally require stabilization to retain activity or viability in a dry form. A number of industrial products, such as vaccines, probiotics and biopesticides have been produced as dry preparations. The same methods and materials used for stabilizing commercial microbial products may be applicable to preserving biothreat pathogens in a dry form. This is a likely step that may be encountered when looking at samples from terrorism attempts since only spores, such as those from Bacillus anthracis, are inherently stable when dried. The stabilizers for microbial preparations generally include one or more small carbohydrates. Different formulations have been reported for different industrial products and are often determined empirically. However sugar alcohols (mannitol and sorbitol) and disaccharides (lactose, sucrose and trehalose) are the common constituents of these formulations. We have developed an analytical method for sample preparation and detection of these simple carbohydrates using two complementary analytical tools, MALDI-MS and GC-MS. The native carbohydrates and other constituents of the formulation are detected by MALDI-MS as a screening tool. A longer and more detailed analysis is then used to specifically identify the carbohydrates by derivatization and GC-MS detection. Both techniques were tested against ten different types of stabilization recipes with Yersinia pestis cell mass cultured on different media types used as the biological component. A number of additional components were included in these formulations including proteins and peptides from serum or milk, polymers (e.g. poly vinyl pyrrolidone - PVP) and detergents (e.g. Tween). The combined method was characterized to determine several figures of merit. The accuracy of the method was 98% for MALDI-MS and 100% for GC-MS. The repeatability for detection of carbohydrates by MALDI-MS was determined to be 96%. The repeatability of compound identification by GC-MS was

Screening of Satureja subspicata Vis. Honey by HPLC-DAD, GC-FID/MS and UV/VIS: Prephenate Derivatives as Biomarkers.

Science.gov (United States)

Jerković, Igor; Kranjac, Marina; Marijanović, Zvonimir; Zekić, Marina; Radonić, Ani; Tuberoso, Carlo Ignazio Giovanni

2016-03-21

The samples of Satureja subspicata Vis. honey were confirmed to be unifloral by melissopalynological analysis with the characteristic pollen share from 36% to 71%. Bioprospecting of the samples was performed by HPLC-DAD, GC-FID/MS, and UV/VIS. Prephenate derivatives were shown to be dominant by the HPLC-DAD analysis, particularly phenylalanine (167.8 mg/kg) and methyl syringate (MSYR, 114.1 mg/kg), followed by tyrosine and benzoic acid. Higher amounts of MSYR (3-4 times) can be pointed out for distinguishing S. subspicata Vis. honey from other Satureja spp. honey types. GC-FID/MS analysis of ultrasonic solvent extracts of the samples revealed MSYR (46.68%, solvent pentane/Et2O 1:2 (v/v); 52.98%, solvent CH2Cl2) and minor abundance of other volatile prephenate derivatives, as well as higher aliphatic compounds characteristic of the comb environment. Two combined extracts (according to the solvents) of all samples were evaluated for their antioxidant properties by FRAP and DPPH assay; the combined extracts demonstrated higher activity (at lower concentrations) in comparison with the average honey sample. UV/VIS analysis of the samples was applied for determination of CIE Lab colour coordinates, total phenolics (425.38 mg GAE/kg), and antioxidant properties (4.26 mmol Fe(2+)/kg (FRAP assay) and 0.8 mmol TEAC/kg (DDPH assay)).

Single-run determination of polybrominated diphenyl ethers (PBDEs) di- to deca-brominated in fish meal, fish oil and fish feed by isotope dilution: Application of automated sample purification and gas chromatography/ion trap tandem mass spectrometry (GC/ITMS)

International Nuclear Information System (INIS)

Blanco, Sonia Lucia; Vieites, Juan M.

2010-01-01

The present paper describes the application of automated cleanup and fractionation procedures of the Power Prep system (Fluid Management Systems) for the determination of polybrominated diphenyl ethers (PBDEs) in feeding stuffs and fish meal and oil. Gas chromatography (GC) separation followed by ion trap tandem mass spectrometry detection in EI mode (ITMS) allowed the analysis of di- to deca-BDEs in the samples matrices used in fish aquaculture. The method developed enabled the determination of 26 native PBDE congeners and 11 13 C 12 -labelled congeners, including deca-BDE 209, in a single-run analysis, using isotope dilution. The automated cleanup, consisting of a succession of multilayer silica and basic alumina columns previously applied by Wyrzykowska et al. (2009) in combustion flue gas, was succesfully applied in our complex matrices. The method allowed an increase in productivity, i.e. lower time was required to process samples, and simultaneous purification of several samples was achieved at a time, reducing analyst dedication and human error input. Average recoveries of 43-96% were obtained. GC/ITMS can overcome the complexity originating from the sample matrix, eliminating matrix effects by tandem MS, to enable the detection of congeners penta- to nona-BDEs where interferent masses were present. The provisional detection limits, estimated in the samples, were 5-30 pg for di-, tri-, tetra-, and penta-BDEs, 20-65 pg for hexa-, hepta-, octa- and nona-BDEs, and 105 pg for deca-BDE. Reduction of deca-BDE 209 blank values is of concern to ongoing research. Good accuracy was obtained by application of the whole procedure, representing an efficient, low-cost and fast alternative for routine analyses.

Evaluation of immunogenicity and safety of the new tetanus-reduced diphtheria (Td) vaccines (GC1107) in healthy Korean adolescents: a phase II, double-blind, randomized, multicenter clinical trial.

Science.gov (United States)

Rhim, Jung-Woo; Lee, Kyung-Yil; Kim, Sang-Yong; Kim, Jong-Hyun; Kim, Hyun-Hee; Kim, Hwang Min; Choi, Young-Youn; Ma, Sang-Hyuk; Kim, Dong-Ho; Ahn, Dong Ho; Kang, Jin-Han

2013-04-01

This phase II clinical trial was conducted to compare the immunogenicity and safety of a newly developed tetanus-reduced diphtheria (Td) vaccine (GC1107-T5.0 and GC1107-T7.5) and control vaccine. This study was also performed to select the proper dose of tetanus toxoid in the new Td vaccines. Healthy adolescents aged between 11 and 12 yr participated in this study. A total of 130 subjects (44 GC1107-T5.0, 42 GC1107-T7.5 and 44 control vaccine) completed a single dose of vaccination. Blood samples were collected from the subjects before and 4 weeks after the vaccination. In this study, all subjects (100%) in both GC1107-T5.0 and GC1107-T7.5 groups showed seroprotective antibody levels (≥ 0.1 U/mL) against diphtheria or tetanus toxoids. After the vaccination, the geometric mean titer (GMT) against diphtheria was significantly higher in Group GC1107-T5.0 (6.53) and GC1107-T7.5 (6.11) than in the control group (3.96). The GMT against tetanus was 18.6 in Group GC1107-T5.0, 19.94 in GC1107-T7.5 and 19.01 in the control group after the vaccination. In this study, the rates of local adverse reactions were 67.3% and 59.1% in GC1107-T5.0 and GC1107-7.5, respectively. No significant differences in the number of adverse reactions, prevalence and degree of severity of the solicited and unsolicited adverse reactions were observed among the three groups. Thus, both newly developed Td vaccines appear to be safe and show good immunogenicity. GC1107-T5.0, which contains relatively small amounts of tetanus toxoid, has been selected for a phase III clinical trial.

Degalactosylated/desialylated human serum containing GcMAF induces macrophage phagocytic activity and in vivo antitumor activity.

Science.gov (United States)

Kuchiike, Daisuke; Uto, Yoshihiro; Mukai, Hirotaka; Ishiyama, Noriko; Abe, Chiaki; Tanaka, Daichi; Kawai, Tomohito; Kubo, Kentaro; Mette, Martin; Inui, Toshio; Endo, Yoshio; Hori, Hitoshi

2013-07-01

The group-specific component protein-derived macrophage-activating factor (GcMAF) has various biological activities, such as macrophage activation and antitumor activity. Clinical trials of GcMAF have been carried out for metastatic breast cancer, prostate cancer, and metastatic colorectal cancer. In this study, despite the complicated purification process of GcMAF, we used enzymatically-treated human serum containing GcMAF with a considerable macrophage-stimulating activity and antitumor activity. We detected GcMAF in degalactosylated/desialylated human serum by western blotting using an anti-human Gc globulin antibody, and Helix pomatia agglutinin lectin. We also found that GcMAF-containing human serum significantly enhanced the phagocytic activity of mouse peritoneal macrophages and extended the survival time of mice bearing Ehrlich ascites tumors. We demonstrated that GcMAF-containing human serum can be used as a potential macrophage activator for cancer immunotherapy.

Hantavirus Gc induces long-term immune protection via LAMP-targeting DNA vaccine strategy.

Science.gov (United States)

Jiang, Dong-Bo; Zhang, Jin-Peng; Cheng, Lin-Feng; Zhang, Guan-Wen; Li, Yun; Li, Zi-Chao; Lu, Zhen-Hua; Zhang, Zi-Xin; Lu, Yu-Chen; Zheng, Lian-He; Zhang, Fang-Lin; Yang, Kun

2018-02-01

Hemorrhagic fever with renal syndrome (HFRS) occurs widely throughout Eurasia. Unfortunately, there is no effective treatment, and prophylaxis remains the best option against the major pathogenic agent, hantaan virus (HTNV), which is an Old World hantavirus. However, the absence of cellular immune responses and immunological memory hampers acceptance of the current inactivated HFRS vaccine. Previous studies revealed that a lysosome-associated membrane protein 1 (LAMP1)-targeting strategy involving a DNA vaccine based on the HTNV glycoprotein Gn successfully conferred long-term immunity, and indicated that further research on Gc, another HTNV antigen, was warranted. Plasmids encoding Gc and lysosome-targeted Gc, designated pVAX-Gc and pVAX-LAMP/Gc, respectively, were constructed. Proteins of interest were identified by fluorescence microscopy following cell line transfection. Five groups of 20 female BALB/c mice were subjected to the following inoculations: inactivated HTNV vaccine, pVAX-LAMP/Gc, pVAX-Gc, and, as the negative controls, pVAX-LAMP or the blank vector pVAX1. Humoral and cellular immunity were assessed by enzyme-linked immunosorbent assays (ELISAs) and 15-mer peptide enzyme-linked immunospot (ELISpot) epitope mapping assays. Repeated immunization with pVAX-LAMP/Gc enhanced adaptive immune responses, as demonstrated by the specific and neutralizing antibody titers and increased IFN-γ production. The inactivated vaccine induced a comparable humoral reaction, but the negative controls only elicited insignificant responses. Using a mouse model of HTNV challenge, the in vivo protection conferred by the inactivated vaccine and Gc-based constructs (with/without LAMP recombination) was confirmed. Evidence of pan-epitope reactions highlighted the long-term cellular response to the LAMP-targeting strategy, and histological observations indicated the safety of the LAMP-targeting vaccines. The long-term protective immune responses induced by pVAX-LAMP/Gc may be

In search of ancient biomarkers: Using femtosecond - Laser Desorption Post Ionization - Mass Spectrometry (fs-LDPI-MS) to map organic compounds within ca. 2.7 Ga samples from the Abitibi greenstone belt, Ontario, Canada

Science.gov (United States)

Pasterski, M. J.; Barry, G.; Hanley, L.; Kenig, F. P. H.

2016-12-01

One of the major challenges within the field of organic geochemistry is to determine whether an observed biomarker signature was emplaced during sedimentation (indigenous), after sedimentation via the post-depositional migration of fluids (non-indigenous), or during sampling, storage, or analysis (contaminant). Current geochemical techniques (e.g. gas chromatography-mass spectrometry, GC-MS and GCxGC-MS) can effectively determine the composition and structure of the organic constituents of a sample. However, because of the multiple preparatory steps necessary prior to GC-MS analysis (sample crushing, solvent extraction, organic fraction separation) it is impossible to precisely determine the spatial relationship between the host sample and the organic molecules within. We used an MS imaging method developed by Prof. Luke Hanley at the University of Illinois at Chicago, femtosecond-laser desorption post ionization-MS (fs-LDPI-MS), to map the organics within previously characterized ca.2.7 billion year old (Ga) metasediments from the Abitibi greenstone belt near Timmins, ON, Canada. We then compared the MS images to petrographic observations that displayed the distribution of mineral species with well constrained mineralization ages as well as fluid inclusions within the samples. Fluid inclusions are formed during mineralization and have the ability to remain intact over long timescales (up to billions of years), protecting the fluids inside from the introduction of non-indigenous and contaminant biomarkers. Although migrating post-depositional fluids can remineralize sediments, fluid inclusions associated with secondary additions are focused along grain boundaries and microfractures (secondary inclusions), thus, inclusions which are located within grain boundaries can be considered primary and the age of their formation can be determined relative to the host rock. Preliminary results indicate that previously observed biomarkers may be linked to a series of

Laser ablation-combustion-GC-IRMS--a new method for online analysis of intra-annual variation of delta13C in tree rings.

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Schulze, Brigit; Wirth, Christian; Linke, Petra; Brand, Willi A; Kuhlmann, Iris; Horna, Viviana; Schulze, Ernst-Detlef

2004-11-01

We present a new, rapid method for high-resolution online determination of delta13C in tree rings, combining laser ablation (LA), combustion (C), gas chromatography (GC) and isotope ratio mass spectrometry (IRMS) (LA-C-GC-IRMS). Sample material was extracted every 6 min with a UV-laser from a tree core, leaving 40-microm-wide holes. Ablated wood dust was combusted to CO2 at 700 degrees C, separated from other gases on a GC column and injected into an isotope ratio mass spectrometer after removal of water vapor. The measurements were calibrated against an internal and an external standard. The tree core remained intact and could be used for subsequent dendrochronological and dendrochemical analyses. Cores from two Scots pine trees (Pinus sylvestris spp. sibirica Lebed.) from central Siberia were sampled. Inter- and intra-annual patterns of delta13C in whole-wood and lignin-extracted cores were indistinguishable apart from a constant offset, suggesting that lignin extraction is unnecessary for our method. Comparison with the conventional method (microtome slicing, elemental analysis and IRMS) indicated high accuracy of the LA-C-GC-IRMS measurements. Patterns of delta13C along three parallel ablation lines on the same core showed high congruence. A conservative estimate of the precision was +/- 0.24 per thousand. Isotopic patterns of the two Scots pine trees were broadly similar, indicating a signal related to the forest stand's climate history. The maximum variation in delta13C over 22 years was about 5 per thousand, ranging from -27 to -22.3 per thousand. The most obvious pattern was a sharp decline in delta13C during latewood formation and a rapid increase with spring early growth. We conclude that the LA-C-GC-IRMS method will be useful in elucidating short-term climate effects on the delta13C signal in tree rings.

Development and Validation of an LC-MS/MS Method and Comparison with a GC-MS Method to Measure Phenytoin in Human Brain Dialysate, Blood, and Saliva

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Raphael Hösli

2018-01-01

Full Text Available Phenytoin (PHT is one of the most often used critical dose drugs, where insufficient or excessive dosing can have severe consequences such as seizures or toxicity. Thus, the monitoring and precise measuring of PHT concentrations in patients is crucial. This study develops and validates an LC-MS/MS method for the measurement of phenytoin concentrations in different body compartments (i.e., human brain dialysate, blood, and saliva and compares it with a formerly developed GC-MS method that measures PHT in the same biological matrices. The two methods are evaluated and compared based on their analytical performance, appropriateness to analyze human biological samples, including corresponding extraction and cleanup procedures, and their validation according to ISO 17025/FDA Guidance for Industry. The LC-MS/MS method showed a higher performance compared with the GC-MS method. The LC-MS/MS was more sensitive, needed a smaller sample volume (25 µL and less chemicals, was less time consuming (cleaning up, sample preparation, and analysis, and resulted in a better LOD ( 0.995 for all tested matrices (blood, saliva, and dialysate. For larger sample numbers as in pharmacokinetic/pharmacodynamic studies and for bedside as well as routine analyses, the LC-MS/MS method offers significant advantages over the GC-MS method.

Unconventionally prepared TiO2/g-C3N4 photocatalysts for photocatalytic decomposition of nitrous oxide

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Troppová, Ivana; Šihor, Marcel; Reli, Martin; Ritz, Michal; Praus, Petr; Kočí, Kamila

2018-02-01

The TiO2/g-C3N4 nanocomposites with the various TiO2:g-C3N4 weight ratios from 1:1 to 1:3 were prepared unconventionally by pressurized hot water processing in a flow regime. The parent TiO2 and g-C3N4 was prepared by thermal hydrolysis and thermal annealing, respectively. The nanocomposites as well as parent TiO2 and g-C3N4 were characterized using several complementary characterization methods and investigated in the photocatalytic decomposition of N2O under UVA (λ = 365 nm) irradiation. All the prepared TiO2/g-C3N4 nanocomposites showed higher photocatalytic activity in comparison with the pure g-C3N4 and chiefly pure TiO2. The photocatalytic activity of TiO2/g-C3N4 nanocomposites was decreasing in the following sequence: TiO2/g-C3N4 (1:3) > TiO2/g-C3N4 (1:2) > TiO2/g-C3N4 (1:1). In comparison with the parent TiO2 or g-C3N4, the TiO2/g-C3N4 nanocomposites' photocatalytic capability was significantly enhanced by coupling TiO2 with g-C3N4. The generation of TiO2/g-C3N4 Z-scheme photocatalyst mainly benefited from the effective separation of photoinduced electron-hole pairs and the extended optical absorption range. The TiO2/g-C3N4 (1:3) nanocomposite showed the best photocatalytic behavior in a consequence of the optimal weight ratio of TiO2:g-C3N4 and the lowest band gap energy from all nanocomposites. The N2O conversion in its presence was 70.6% after 20 h of UVA irradiation.

Analysis of residual solvents in PET radiopharmaceuticals by GC

International Nuclear Information System (INIS)

Li Yungang; Zhang Xiaojun; Liu Jian; Tian Jiahe; Zhang Jinming

2013-01-01

The residual solvents in PET radiopharmaceuticals were analyzed by GC, which were acetonitrile, ethanol, N, N-dimethylethanolamine (DMEA), dimethylsulfoxide (DMSO). The standard curves were established with the AT-624 capillary column at GC, and the sensitivity of acetonitrile and ethanol were 0.004-0.320 g/L and 0.010-0.120 g/L respectively. The residual solvents of acetonitrile, ethanol, DMEA and DMSO in PET radio- pharmaceuticals were analyzed by GC. The linearity were 0.9994, 0.9999, 0.9997, 0.999 6 respectively. The residual of acetonitrile were (0.0313±0.0433), (0.0829±0.0668), (0.0156±0.0059), (0.0254±0.0266) g/L in 18 F-FDG, 18 F-FLT, 11 C-CFT, 11 C-PIB respectively. The residual of ethanol was (0.0505±0.00528) g/L in 18 F-FDG. The residual of DMSO were (0.0331±0.0180) g/L, (0.0238±0.0100) g/L in 18 F-W372 and 11 C-DTBZ respectively. The residual of DMEA was (0.0348±0.0022) g/L in 11 C-Choline. The survived of organic solvent in PET radiopharmaceuticals can be analyzed with GC directly. The results showed that the QC should be done in PET radiopharmaceuticals purity with semi-HPLC to avoid the high residual. (authors)

PyMS: a Python toolkit for processing of gas chromatography-mass spectrometry (GC-MS data. Application and comparative study of selected tools

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O'Callaghan Sean

2012-05-01

as well or better than leading software packages. We demonstrate data processing scenarios simple to implement in PyMS, yet difficult to achieve with many conventional GC-MS data processing software. Automated sample processing and quantitation with PyMS can provide substantial time savings compared to more traditional interactive software systems that tightly integrate data processing with the graphical user interface.

A method for the determination of acrylamide in a broad variety of processed foods by GC-MS using xanthydrol derivatization.

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Yamazaki, Kumiko; Isagawa, Satoshi; Kibune, Nobuyuki; Urushiyama, Tetsuo

2012-01-01

A novel GC-MS method was developed for the determination of acrylamide, which is applicable to a variety of processed foods, including potato snacks, corn snacks, biscuits, instant noodles, coffee, soy sauces and miso (fermented soy bean paste). The method involves the derivatization of acrylamide with xanthydrol instead of a bromine compound. Isotopically labelled acrylamide (d₃-acrylamide) was used as the internal standard. The aqueous extract from samples was purified using Sep-Pak™ C₁₈ and Sep-Pak™ AC-2 columns. For amino acid-rich samples, such as miso or soy sauce, an Extrelut™ column was used for purification or extraction. After reaction with xanthydrol, the resultant N-xanthyl acrylamide was determined by GC-MS. The method was validated for various food matrices and showed good linearity, precision and trueness. The limit of detection and limit of quantification ranged 0.5-5 and 5-20 µg kg⁻¹), respectively. The developed method was applied as an exploratory survey of acrylamide in Japanese foods and the method was shown to be applicable for all samples tested.

Utilization of long duration high-volume sampling coupled to SPME-GC-MS/MS for the assessment of airborne pesticides variability in an urban area (Strasbourg, France) during agricultural application.

Science.gov (United States)

Liaud, Céline; Brucher, Michel; Schummer, Claude; Coscollà, Clara; Wolff, Hélène; Schwartz, Jean-Jacques; Yusà, Vicent; Millet, Maurice

2016-10-02

Atmospheric samples have been collected between 14 March and 12 September 2012 on a 2-week basis (15 days of sampling and exchange of traps each 7 days) in Strasbourg (east of France) for the analysis of 43 pesticides. Samples (particle and gas phases) were separately extracted using Accelerated Solvent Extraction (ASE) and pre-concentrated by Solid Phase Micro-Extraction (SPME) before analysis by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Four SPME consecutive injections at distinct temperatures were made in order to increase the sensitivity of detection for the all monitored pesticides. Currently used detected pesticides can be grouped in four classes; those used in maize crops (acetochlor, benoxacor, dicamba, s-metolachlor, pendimethalin, and bromoxynil), in cereal crops (benoxacor, chlorothalonil, fenpropimorph, and propiconazole), in vineyards (tebuconazole), and as herbicides for orchards, meadows of green spaces (2,4-MCPA, trichlopyr). This is in accordance with the diversity of crops found in the Alsace region and trends observed are in accordance with the period of application of these pesticides. Variations observed permit also to demonstrate that the long time sampling duration used in this study is efficient to visualize temporal variations of airborne pesticides concentrations. Then, long time high-volume sampling could be a simple method permitting atmospheric survey of atmospheric contamination without any long analysis time and consequently low cost.

Characterization of a Carbon Nanotube Field Emission Electron Gun for the VAPoR Miniaturized Pyrolysis-Time-of-Flight Mass Spectrometer

Science.gov (United States)

Getty, Stephanie; Li, Mary; Costen, Nicholas; Hess, Larry; Feng, Steve; King, Todd; Brinckerhoff, William; Mahaffy, Paul; Glavin, Daniel

2009-01-01

We are developing the VAPoR (Volatile Analysis by Pyrolysis of Regolith) instrument towards studying soil composition, volatiles, and trapped noble gases in the polar regions of the Moon. VAPOR will ingest a soil sample and conduct analysis by pyrolysis and time-of-flight mass spectrometry (ToF-MS). Here, we describe miniaturization efforts within this development, including a carbon nanotube (CNT) field emission electron gun that is under consideration for use as the electron impact ionization source for the ToF-MS.

The discriminant pixel approach: a new tool for the rational interpretation of GCxGC-MS chromatograms.

Science.gov (United States)

Vial, Jérôme; Pezous, Benoît; Thiébaut, Didier; Sassiat, Patrick; Teillet, Béatrice; Cahours, Xavier; Rivals, Isabelle

2011-01-30

GCxGC is now recognized as the most suited analytical technique for the characterization of complex mixtures of volatile compounds; it is implemented worldwide in academic and industrial laboratories. However, in the frame of comprehensive analysis of non-target analytes, going beyond the visual examination of the color plots remains challenging for most users. We propose a strategy that aims at classifying chromatograms according to the chemical composition of the samples while determining the origin of the discrimination between different classes of samples: the discriminant pixel approach. After data pre-processing and time-alignment, the discriminatory power of each chromatogram pixel for a given class was defined as its correlation with the membership to this class. Using a peak finding algorithm, the most discriminant pixels were then linked to chromatographic peaks. Finally, crosschecking with mass spectrometry data enabled to establish relationships with compounds that could consequently be considered as candidate class markers. This strategy was applied to a large experimental data set of 145 GCxGC-MS chromatograms of tobacco extracts corresponding to three distinct classes of tobacco. Copyright © 2010 Elsevier B.V. All rights reserved.

Urinary amino acid analysis: a comparison of iTRAQ-LC-MS/MS, GC-MS, and amino acid analyzer.

Science.gov (United States)

Kaspar, Hannelore; Dettmer, Katja; Chan, Queenie; Daniels, Scott; Nimkar, Subodh; Daviglus, Martha L; Stamler, Jeremiah; Elliott, Paul; Oefner, Peter J

2009-07-01

Urinary amino acid analysis is typically done by cation-exchange chromatography followed by post-column derivatization with ninhydrin and UV detection. This method lacks throughput and specificity. Two recently introduced stable isotope ratio mass spectrometric methods promise to overcome those shortcomings. Using two blinded sets of urine replicates and a certified amino acid standard, we compared the precision and accuracy of gas chromatography/mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) of propyl chloroformate and iTRAQ derivatized amino acids, respectively, to conventional amino acid analysis. The GC-MS method builds on the direct derivatization of amino acids in diluted urine with propyl chloroformate, GC separation and mass spectrometric quantification of derivatives using stable isotope labeled standards. The LC-MS/MS method requires prior urinary protein precipitation followed by labeling of urinary and standard amino acids with iTRAQ tags containing different cleavable reporter ions distinguishable by MS/MS fragmentation. Means and standard deviations of percent technical error (%TE) computed for 20 amino acids determined by amino acid analyzer, GC-MS, and iTRAQ-LC-MS/MS analyses of 33 duplicate and triplicate urine specimens were 7.27+/-5.22, 21.18+/-10.94, and 18.34+/-14.67, respectively. Corresponding values for 13 amino acids determined in a second batch of 144 urine specimens measured in duplicate or triplicate were 8.39+/-5.35, 6.23+/-3.84, and 35.37+/-29.42. Both GC-MS and iTRAQ-LC-MS/MS are suited for high-throughput amino acid analysis, with the former offering at present higher reproducibility and completely automated sample pretreatment, while the latter covers more amino acids and related amines.

The study of fingerprint characteristics of Dayi Pu-Erh tea using a fully automatic HS-SPME/GC-MS and combined chemometrics method.

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Shidong Lv

Full Text Available The quality of tea is presently evaluated by the sensory assessment of professional tea tasters, however, this approach is both inconsistent and inaccurate. A more standardized and efficient method is urgently needed to objectively evaluate tea quality. In this study, the chemical fingerprint of 7 different Dayi Pu-erh tea brands and 3 different Ya'an tea brands on the market were analyzed using fully automatic headspace solid-phase microextraction (HS-SPME combined with gas chromatography-mass spectrometry (GC-MS. A total of 78 volatiles were separated, among 75 volatiles were identified by GC-MS in seven Dayi Pu-erh teas, and the major chemical components included methoxyphenolic compounds, hydrocarbons, and alcohol compounds, such as 1,2,3-trimethoxybenzene, 1,2,4-trimethoxybenzene, 2,6,10,14-tetramethyl-pentadecane, linalool and its oxides, α-terpineol, and phytol. The overlapping ratio of peaks (ORP of the chromatogram in the seven Dayi Pu-erh tea samples was greater than 89.55%, whereas the ORP of Ya'an tea samples was less than 79.10%. The similarity and differences of the Dayi Pu-erh tea samples were also characterized using correlation coefficient similarity and principal component analysis (PCA. The results showed that the correlation coefficient of similarity of the seven Dayi Pu-erh tea samples was greater than 0.820 and was gathered in a specific area, which showed that samples from different brands were basically the same, despite have some slightly differences of chemical indexes was found. These results showed that the GC-MS fingerprint combined with the PCA approach can be used as an effective tool for the quality assessment and control of Pu-erh tea.

GC-ASM: Synergistic Integration of Graph-Cut and Active Shape Model Strategies for Medical Image Segmentation.

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Chen, Xinjian; Udupa, Jayaram K; Alavi, Abass; Torigian, Drew A

2013-05-01

Image segmentation methods may be classified into two categories: purely image based and model based. Each of these two classes has its own advantages and disadvantages. In this paper, we propose a novel synergistic combination of the image based graph-cut (GC) method with the model based ASM method to arrive at the GC-ASM method for medical image segmentation. A multi-object GC cost function is proposed which effectively integrates the ASM shape information into the GC framework. The proposed method consists of two phases: model building and segmentation. In the model building phase, the ASM model is built and the parameters of the GC are estimated. The segmentation phase consists of two main steps: initialization (recognition) and delineation. For initialization, an automatic method is proposed which estimates the pose (translation, orientation, and scale) of the model, and obtains a rough segmentation result which also provides the shape information for the GC method. For delineation, an iterative GC-ASM algorithm is proposed which performs finer delineation based on the initialization results. The proposed methods are implemented to operate on 2D images and evaluated on clinical chest CT, abdominal CT, and foot MRI data sets. The results show the following: (a) An overall delineation accuracy of TPVF > 96%, FPVF ASM for different objects, modalities, and body regions. (b) GC-ASM improves over ASM in its accuracy and precision to search region. (c) GC-ASM requires far fewer landmarks (about 1/3 of ASM) than ASM. (d) GC-ASM achieves full automation in the segmentation step compared to GC which requires seed specification and improves on the accuracy of GC. (e) One disadvantage of GC-ASM is its increased computational expense owing to the iterative nature of the algorithm.

Gc-protein-derived macrophage activating factor counteracts the neuronal damage induced by oxaliplatin.

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Morucci, Gabriele; Branca, Jacopo J V; Gulisano, Massimo; Ruggiero, Marco; Paternostro, Ferdinando; Pacini, Alessandra; Di Cesare Mannelli, Lorenzo; Pacini, Stefania

2015-02-01

Oxaliplatin-based regimens are effective in metastasized advanced cancers. However, a major limitation to their widespread use is represented by neurotoxicity that leads to peripheral neuropathy. In this study we evaluated the roles of a proven immunotherapeutic agent [Gc-protein-derived macrophage activating factor (GcMAF)] in preventing or decreasing oxaliplatin-induced neuronal damage and in modulating microglia activation following oxaliplatin-induced damage. The effects of oxaliplatin and of a commercially available formula of GcMAF [oleic acid-GcMAF (OA-GcMAF)] were studied in human neurons (SH-SY5Y cells) and in human microglial cells (C13NJ). Cell density, morphology and viability, as well as production of cAMP and expression of vascular endothelial growth factor (VEGF), markers of neuron regeneration [neuromodulin or growth associated protein-43 (Gap-43)] and markers of microglia activation [ionized calcium binding adaptor molecule 1 (Iba1) and B7-2], were determined. OA-GcMAF reverted the damage inflicted by oxaliplatin on human neurons and preserved their viability. The neuroprotective effect was accompanied by increased intracellular cAMP production, as well as by increased expression of VEGF and neuromodulin. OA-GcMAF did not revert the effects of oxaliplatin on microglial cell viability. However, it increased microglial activation following oxaliplatin-induced damage, resulting in an increased expression of the markers Iba1 and B7-2 without any concomitant increase in cell number. When neurons and microglial cells were co-cultured, the presence of OA-GcMAF significantly counteracted the toxic effects of oxaliplatin. Our results demonstrate that OA-GcMAF, already used in the immunotherapy of advanced cancers, may significantly contribute to neutralizing the neurotoxicity induced by oxaliplatin, at the same time possibly concurring to an integrated anticancer effect. The association between these two powerful anticancer molecules would probably produce

Questioning the role of actinfree Gc-Globulin as actin scavenger in neurodegenerative central nervous system disease: relationship to S-100B levels and blood-brain barrier function.

Science.gov (United States)

Gressner, Olav A; Schifflers, Marie-Claire; Kim, Philipp; Heuts, Leo; Lahme, Birgit; Gressner, Axel M

2009-02-01

Preliminary studies report on significantly higher levels of the major cytoskeleton protein actin in CSF of patients with neurodegenerative conditions and that the dynamics of these levels obviously correlates with disease progression and clinical disability. One of the primary functions of actinfree Gc-Globulin is to bind and neutralize extracellular monomeric actin, released into the circulation by necrotic or ruptured cells, and thus ameliorating the clinical outcome in situations of severe organ damage. This is the first study to investigate actinfree Gc-Globulin and S100-B levels (as reliable marker of neurodegeneration) in paired CSF and serum samples of patients with multietiological CNS diseases. 42% of all patients with CNS disease displayed serum concentrations of actinfree Gc-Globulin above the established reference range. CSF concentrations of actinfree Gc-Globulin and S100-B were positively correlated with the severity of blood-brain barrier (BBB) dysfunction. Furthermore, patients with severe BBB dysfunction presented a higher percentage of intrathecal synthesis of actinfree Gc-Globulin compared to patients with mild to moderate dysfunction and to patients with normal BBB function. Representative longitudinal data from selected patients demonstrated an inverse behaviour of actinfree Gc-Globulin and S100-B CSF concentrations, suggesting a consumption of the actin scavenger capacity of Gc-Globulin in times of increased neuronal damage. This presumption was supported by the fact that those conditions associated with a severe neuronal damage, in particular CNS trauma, and highest S100-B concentrations simultaneously displayed lowest actinfree Gc-Globulin levels, and thus residual actin binding capacity of Gc-Globulin. In summary, our data propose a function of actinfree Gc-Globulin also in the clearance of actin filaments from CSF of patients with neuronal damage. However, active recruitment of hepatic derived actinfree Gc-Globulin to the site of CNS

Hydrogen (H) Isotope Composition of Type II Kerogen Extracted by Pyrolysis-GC-MS-IRMS: Terrestrial Shale Deposits as Martian Analogs

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Socki, Richard A.; Pernia, Denet; Evans, Michael; Fu, Qi; Bissada, Kadry K.; Curiale, Joseph A.; Niles, Paul B.

2014-01-01

Described here is a technique for H isotope analysis of organic compounds pyrolyzed from kerogens isolated from gas- and liquids-rich shales. Application of this technique will progress the understanding of the use of H isotopes not only in potential kerogen occurrences on Mars, but also in terrestrial oil and gas resource plays. H isotope extraction and analyses were carried out utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make qualitative and semi-quantitative compositional measurements of these products. Kerogen samples from five different basins (type II and II-S) were dehydrated (heated to 80 C overnight under vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C), which quantitatively forms H2. Samples ranging from 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. and separated on a Poraplot Q GC column. H isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight. H2O average delta D = -215.2 per mille (V-SMOW), ranging from - 271.8 per mille for the Marcellus Shale to -51.9 per mille for a Polish shale. Higher molecular weight compounds like toluene (C7H8) have an average delta D of -89.7 per mille, ranging from -156.0 per mille for the Barnett Shale to -50.0 per mille for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during basin formation. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleoenvironmental conditions. Alternatively, our data may be an indication of H isotope exchange with

Analysis of Phenolic and Cyclic Compounds in Plants Using Derivatization Techniques in Combination with GC-MS-Based Metabolite Profiling

Directory of Open Access Journals (Sweden)

Jens Rohloff

2015-02-01

Full Text Available Metabolite profiling has been established as a modern technology platform for the description of complex chemical matrices and compound identification in biological samples. Gas chromatography coupled with mass spectrometry (GC-MS in particular is a fast and accurate method widely applied in diagnostics, functional genomics and for screening purposes. Following solvent extraction and derivatization, hundreds of metabolites from different chemical groups can be characterized in one analytical run. Besides sugars, acids, and polyols, diverse phenolic and other cyclic metabolites can be efficiently detected by metabolite profiling. The review describes own results from plant research to exemplify the applicability of GC-MS profiling and concurrent detection and identification of phenolics and other cyclic structures.

Preparation of WO3/g-C3N4 composites and their application in oxidative desulfurization

International Nuclear Information System (INIS)

Zhao, Rongxiang; Li, Xiuping; Su, Jianxun; Gao, Xiaohan

2017-01-01

Highlights: • The WO 3 /g-C 3 N 4 was successfully synthesized through simple calcination. • The process is simple and the cost raw materials is cheap. • The WO 3 /g-C 3 N 4 firstly applied to ODS. • The desulpurization rate of WO 3 /g-C 3 N 4 may attach to 91.2%. • Five recycles of WO 3 /g-C 3 N 4 still attach to 89.5% due to heterogeneous catalysis. - Abstract: WO 3 /graphitic carbon nitride (g-C 3 N 4 ) composites were successfully synthesized through direct calcining of a mixture of WO 3 and g-C 3 N 4 at 400 °C for 2 h. The WO 3 was prepared by calcination of phosphotungstic acid at 550 °C for 4 h, and the g-C 3 N 4 was obtained by calcination of melamine at 520 °C for 4 h. The WO 3 /g-C 3 N 4 composites were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), and Brunner−Emmett−Teller analysis (BET). The WO 3 /g-C 3 N 4 composites exhibited stronger XRD peaks of WO 3 and g-C 3 N 4 than the WO 3 and pure g-C 3 N 4 . In addition, two WO 3 peaks at 25.7° and 26.6° emerged for the 36% −WO 3 /g-C 3 N 4 composite. This finding indicated that WO 3 was highly dispersed on the surface of the g-C 3 N 4 nanosheets and interacted with the nanosheets, which resulted in the appearance of (012) and (022) planes of WO 3 . The WO 3 /g-C 3 N 4 composite also exhibited a larger specific surface area and higher degree of crystallization than WO 3 or pure g-C 3 N 4 , which resulted in high catalytic activity of the catalyst. Desulfurization experiments demonstrated that the desulfurization rate of dibenzothiophene (DBT) in model oil reached 91.2% under optimal conditions. Moreover, the activity of the catalyst was not significantly decreased after five recycles.

Immunotherapy of metastatic colorectal cancer with vitamin D-binding protein-derived macrophage-activating factor, GcMAF.

Science.gov (United States)

Yamamoto, Nobuto; Suyama, Hirofumi; Nakazato, Hiroaki; Yamamoto, Nobuyuki; Koga, Yoshihiko

2008-07-01

Serum vitamin D binding protein (Gc protein) is the precursor for the principal macrophage-activating factor (MAF). The MAF precursor activity of serum Gc protein of colorectal cancer patients was lost or reduced because Gc protein is deglycosylated by serum alpha-N-acetylgalactosaminidase (Nagalase) secreted from cancerous cells. Deglycosylated Gc protein cannot be converted to MAF, leading to immunosuppression. Stepwise treatment of purified Gc protein with immobilized beta-galactosidase and sialidase generated the most potent macrophage-activating factor (GcMAF) ever discovered, but it produces no side effect in humans. Macrophages treated with GcMAF (100 microg/ml) develop an enormous variation of receptors and are highly tumoricidal to a variety of cancers indiscriminately. Administration of 100 nanogram (ng)/ human maximally activates systemic macrophages that can kill cancerous cells. Since the half-life of the activated macrophages is approximately 6 days, 100 ng GcMAF was administered weekly to eight nonanemic colorectal cancer patients who had previously received tumor-resection but still carried significant amounts of metastatic tumor cells. As GcMAF therapy progressed, the MAF precursor activities of all patients increased and conversely their serum Nagalase activities decreased. Since serum Nagalase is proportional to tumor burden, serum Nagalase activity was used as a prognostic index for time course analysis of GcMAF therapy. After 32-50 weekly administrations of 100 ng GcMAF, all colorectal cancer patients exhibited healthy control levels of the serum Nagalase activity, indicating eradication of metastatic tumor cells. During 7 years after the completion of GcMAF therapy, their serum Nagalase activity did not increase, indicating no recurrence of cancer, which was also supported by the annual CT scans of these patients.

Predicting refinery effluent toxicity on the basis of hydrocarbon composition determined by GCxGC analysis

Energy Technology Data Exchange (ETDEWEB)

Whale, G. [and others

2013-04-15

A high resolution analytical method for determining hydrocarbon blocks in petroleum products by comprehensive two-dimensional gas chromatography (GCxGC) was used for the analysis of petroleum hydrocarbons extracted from refinery effluents. From 105 CONCAWE refineries in Europe 111 refinery effluents were collected in the period June 2008 to March 2009 (CONCAWE, 2010). The effluents were analysed for metals, standard effluent parameters (including Chemical Oxygen Demand (COD), Biochemical Oxygen Demand (BOD), oil in water (OiW), GCxGC speciated hydrocarbons, BTEX (Benzene, Toluene, Ethylbenzene, and Xylenes) and volatile organic compounds. This report describes the subsequent analysis of the GCxGC data, as described in hydrocarbon blocks, and uses the PETROTOX model, to predict the environmental toxicity (i.e. ecotoxicity) of the discharged effluents. A further analysis was undertaken to address the potential environmental impact of these predicted effects initially using default dilution factors and then,when necessary site specific factors. The report describes all the methods used to arrive at the predictions, and shows that for the majority of refinery effluents direct toxicity effects in the effluents are not anticipated. Furthermore, when applying either the EU Risk Assessment Technical Guidance Document (TGD) default dilution factors or site specific dilution factors, none of the refineries are predicted to exerting either acute or chronic toxicity to organisms in the receiving aquatic environment, based on their hydrocarbon composition present in the effluent samples.

Biased Gene Conversion and GC-Content Evolution in the Coding Sequences of Reptiles and Vertebrates

Science.gov (United States)

Figuet, Emeric; Ballenghien, Marion; Romiguier, Jonathan; Galtier, Nicolas

2015-01-01

Mammalian and avian genomes are characterized by a substantial spatial heterogeneity of GC-content, which is often interpreted as reflecting the effect of local GC-biased gene conversion (gBGC), a meiotic repair bias that favors G and C over A and T alleles in high-recombining genomic regions. Surprisingly, the first fully sequenced nonavian sauropsid (i.e., reptile), the green anole Anolis carolinensis, revealed a highly homogeneous genomic GC-content landscape, suggesting the possibility that gBGC might not be at work in this lineage. Here, we analyze GC-content evolution at third-codon positions (GC3) in 44 vertebrates species, including eight newly sequenced transcriptomes, with a specific focus on nonavian sauropsids. We report that reptiles, including the green anole, have a genome-wide distribution of GC3 similar to that of mammals and birds, and we infer a strong GC3-heterogeneity to be already present in the tetrapod ancestor. We further show that the dynamic of coding sequence GC-content is largely governed by karyotypic features in vertebrates, notably in the green anole, in agreement with the gBGC hypothesis. The discrepancy between third-codon positions and noncoding DNA regarding GC-content dynamics in the green anole could not be explained by the activity of transposable elements or selection on codon usage. This analysis highlights the unique value of third-codon positions as an insertion/deletion-free marker of nucleotide substitution biases that ultimately affect the evolution of proteins. PMID:25527834

GC protein-derived macrophage-activating factor decreases α-N-acetylgalactosaminidase levels in advanced cancer patients.

Science.gov (United States)

Thyer, Lynda; Ward, Emma; Smith, Rodney; Branca, Jacopo Jv; Morucci, Gabriele; Gulisano, Massimo; Noakes, David; Eslinger, Robert; Pacini, Stefania

2013-08-01

α- N -acetylgalactosaminidase (nagalase) accumulates in the serum of cancer patients and its activity correlates with tumor burden, aggressiveness and clinical disease progression. The administration of GC protein-derived macrophage-activating factor (GcMAF) to cancer patients with elevated levels of nagalase has been associated with a decrease of serum nagalase activity and with significant clinical benefits. Here, we report the results of the administration of GcMAF to a heterogeneous cohort of patients with histologically diverse, advanced neoplasms, generally considered as "incurable" diseases. In most cases, GcMAF therapy was initiated at late stages of tumor progression. As this is an open-label, non-controlled, retrospective analysis, caution must be employed when establishing cause-effect relationships between the administration GcMAF and disease outcome. However, the response to GcMAF was generally robust and some trends emerged. All patients (n = 20) presented with elevated serum nagalase activity, well above normal values. All patients but one showed a significant decrease of serum nagalase activity upon weekly GcMAF injections. Decreased nagalase activity was associated with improved clinical conditions and no adverse side effects were reported. The observations reported here confirm and extend previous results and pave the way to further studies aimed at assessing the precise role and indications for GcMAF-based anticancer immunotherapy.

Alkylation or Silylation for Analysis of Amino and Non-Amino Organic Acids by GC-MS?

Directory of Open Access Journals (Sweden)

Silas G. Villas-Bôas

2011-01-01

Full Text Available Gas chromatography–mass spectrometry (GC-MS is a widely used analytical technique in metabolomics. GC provides the highest resolution of any standard chromatographic separation method, and with modern instrumentation, retention times are very consistent between analyses. Electron impact ionization and fragmentation is generally reproducible between instruments and extensive libraries of spectra are available that enhance the identification of analytes. The major limitation is the restriction to volatile analytes, and hence the requirement to convert many metabolites to volatile derivatives through chemical derivatization. Here we compared the analytical performance of two derivatization techniques, silylation (TMS and alkylation (MCF, used for the analysis of amino and non-amino organic acids as well as nucleotides in microbial-derived samples. The widely used TMS derivatization method showed poorer reproducibility and instability during chromatographic runs while the MCF derivatives presented better analytical performance. Therefore, alkylation (MCF derivatization seems to be preferable for the analysis of polyfunctional amines, nucleotides and organic acids in microbial metabolomics studies.

Plasma sample based analysis of gastric cancer progression using targeted metabolomics.

Science.gov (United States)

Lario, Sergio; Ramírez-Lázaro, Maria José; Sanjuan-Herráez, Daniel; Brunet-Vega, Anna; Pericay, Carles; Gombau, Lourdes; Junquera, Félix; Quintás, Guillermo; Calvet, Xavier

2017-12-19

Gastric carcinogenesis is a multifactorial process described as a stepwise progression from non-active gastritis (NAG), chronic active gastritis (CAG), precursor lesions of gastric cancer (PLGC) and gastric adenocarcinoma. Gastric cancer (GC) 5-year survival rate is highly dependent upon stage of disease at diagnosis, which is based on endoscopy, biopsy and pathological examinations. Non-invasive GC biomarkers would facilitate its diagnosis at early stages leading to improved GC prognosis. We analyzed plasma samples collected from 80 patients diagnosed with NAG without H. pylori infection (NAG-), CAG with H. pylori infection (CAG+), PLGC and GC. A panel of 208 metabolites including acylcarnitines, amino acids and biogenic amines, sphingolipids, glycerophospholipids, hexoses, and tryptophan and phenylalanine metabolites were quantified using two complementary quantitative approaches: Biocrates AbsoluteIDQ®p180 kit and a LC-MS method designed for the analysis of 29 tryptophan pathway and phenylalanine metabolites. Significantly altered metabolic profiles were found in GC patients that allowing discrimination from NAG-, CAG+ and PLGC patients. Pathway analysis showed significantly altered tryptophan and nitrogen metabolic pathways (FDR P < 0.01). Three metabolites (histidine, tryprophan and phenylacetylglutamine) discriminated between non-GC and GC groups. These metabolic signatures open new possibilities to improve surveillance of PLGC patients using a minimally invasive blood analysis.

Single-run determination of polybrominated diphenyl ethers (PBDEs) di- to deca-brominated in fish meal, fish oil and fish feed by isotope dilution: application of automated sample purification and gas chromatography/ion trap tandem mass spectrometry (GC/ITMS).

Science.gov (United States)

Blanco, Sonia Lucía; Vieites, Juan M

2010-07-05

The present paper describes the application of automated cleanup and fractionation procedures of the Power Prep system (Fluid Management Systems) for the determination of polybrominated diphenyl ethers (PBDEs) in feeding stuffs and fish meal and oil. Gas chromatography (GC) separation followed by ion trap tandem mass spectrometry detection in EI mode (ITMS) allowed the analysis of di- to deca-BDEs in the samples matrices used in fish aquaculture. The method developed enabled the determination of 26 native PBDE congeners and 11 (13)C(12)-labelled congeners, including deca-BDE 209, in a single-run analysis, using isotope dilution. The automated cleanup, consisting of a succession of multilayer silica and basic alumina columns previously applied by Wyrzykowska et al. (2009) [28] in combustion flue gas, was successfully applied in our complex matrices. The method allowed an increase in productivity, i.e. lower time was required to process samples, and simultaneous purification of several samples was achieved at a time, reducing analyst dedication and human error input. Average recoveries of 43-96% were obtained. GC/ITMS can overcome the complexity originating from the sample matrix, eliminating matrix effects by tandem MS, to enable the detection of congeners penta- to nona-BDEs where interferent masses were present. The provisional detection limits, estimated in the samples, were 5-30 pg for di-, tri-, tetra-, and penta-BDEs, 20-65 pg for hexa-, hepta-, octa- and nona-BDEs, and 105 pg for deca-BDE. Reduction of deca-BDE 209 blank values is of concern to ongoing research. Good accuracy was obtained by application of the whole procedure, representing an efficient, low-cost and fast alternative for routine analyses. Copyright 2010 Elsevier B.V. All rights reserved.

Interleukin 6-174 G/C promoter and variable number of tandem repeats (VNTR) gene polymorphisms in sporadic Alzheimer's disease.

Science.gov (United States)

Capurso, Cristiano; Solfrizzi, Vincenzo; Colacicco, Anna Maria; D'Introno, Alessia; Frisardi, Vincenza; Imbimbo, Bruno P; Lorusso, Maria; Vendemiale, Gianluigi; Denitto, Marta; Santamato, Andrea; Seripa, Davide; Pilotto, Alberto; Fiore, Pietro; Capurso, Antonio; Panza, Francesco

2010-02-01

Previous studies examining the association between the interleukin 6 (IL-6)-174 C/G polymorphism and Alzheimer's disease (AD) have yielded conflicting results. Furthermore, the C allele of the IL-6 variable number of tandem repeats (VNTR) polymorphism was associated with a delayed onset and a decreased risk of AD. A total sample of 149 AD patients, and 298 age- and sex-matched unrelated caregivers from Apulia, southern Italy, were genotyped for the apolipoprotein E (APOE) polymorphism, the VNTR polymorphism in the 3' flanking region, and the -174G/C single-nucleotide polymorphism (SNP) in the promoter region of IL-6 gene on chromosome 7. Furthermore, we performed a haplotype analysis on these two polymorphisms on IL-6 locus. IL-6 VNTR and -174G/C allele and genotype frequencies were similar between AD patients and controls, also after stratification for late-onset (> or =65 years) and early-onset (VNTR and -174G/C polymorphisms, not supporting a previous reported additive effect of both IL-6 polymorphisms on AD risk. Our findings did not support a role of IL-6-174 G/C and IL-6 VNTR polymorphisms in the risk of sporadic AD in southern Italy, suggesting that these polymorphisms of IL-6 gene were at most weak genetic determinants of AD. Copyright 2009 Elsevier Inc. All rights reserved.

Desorption electrospray ionisation mass spectrometry: A rapid screening tool for veterinary drug preparations and forensic samples from hormone crime investigations

International Nuclear Information System (INIS)

Nielen, M.W.F.; Hooijerink, H.; Claassen, F.C.; Engelen, M.C. van; Beek, T.A. van

2009-01-01

Hormone and veterinary drug screening and forensics can benefit from the recent developments in desorption electrospray ionisation (DESI) mass spectrometry (MS). In this work the feasibility of DESI application has been studied. Using a linear ion trap or quadrupole time-of-flight (TOF) MS instrument both full-scan and data-dependent collision-induced dissociation MS n spectra were acquired in seconds without sample preparation. Preliminary data are presented for the rapid screening of (pro)hormone supplement samples, an illegal steroid cocktail and forensic samples from veterinary drug investigations. The potential of this DESI approach is clearly demonstrated since compounds observed could be independently confirmed by liquid chromatography/TOFMS with accurate mass measurement, and/or proton nuclear magnetic resonance spectroscopy. Specific concerns related to false-positive and false-negative findings due to limitations in quantification and memory-effects are briefly discussed. It is envisaged that DESI will achieve a prominent role in hormone and veterinary drug analysis in the near future

Desorption electrospray ionisation mass spectrometry: A rapid screening tool for veterinary drug preparations and forensic samples from hormone crime investigations

Energy Technology Data Exchange (ETDEWEB)

Nielen, M.W.F. [RIKILT Institute of Food Safety, P.O. Box 230, 6700 AE Wageningen (Netherlands); Wageningen University, Laboratory of Organic Chemistry, Dreijenplein 8, 6703 HB Wageningen (Netherlands)], E-mail: michel.nielen@wur.nl; Hooijerink, H. [RIKILT Institute of Food Safety, P.O. Box 230, 6700 AE Wageningen (Netherlands); Claassen, F.C. [Wageningen University, Laboratory of Organic Chemistry, Dreijenplein 8, 6703 HB Wageningen (Netherlands); Engelen, M.C. van [RIKILT Institute of Food Safety, P.O. Box 230, 6700 AE Wageningen (Netherlands); Beek, T.A. van [Wageningen University, Laboratory of Organic Chemistry, Dreijenplein 8, 6703 HB Wageningen (Netherlands)

2009-04-01

Hormone and veterinary drug screening and forensics can benefit from the recent developments in desorption electrospray ionisation (DESI) mass spectrometry (MS). In this work the feasibility of DESI application has been studied. Using a linear ion trap or quadrupole time-of-flight (TOF) MS instrument both full-scan and data-dependent collision-induced dissociation MS{sup n} spectra were acquired in seconds without sample preparation. Preliminary data are presented for the rapid screening of (pro)hormone supplement samples, an illegal steroid cocktail and forensic samples from veterinary drug investigations. The potential of this DESI approach is clearly demonstrated since compounds observed could be independently confirmed by liquid chromatography/TOFMS with accurate mass measurement, and/or proton nuclear magnetic resonance spectroscopy. Specific concerns related to false-positive and false-negative findings due to limitations in quantification and memory-effects are briefly discussed. It is envisaged that DESI will achieve a prominent role in hormone and veterinary drug analysis in the near future.

Optimasi Instrumen GC Shimadzu-2014 Terhadap Beberapa Senyawa Metil Ester Asam Lemak (FAME)

OpenAIRE

Tanaty, Muhammad Zaid M. M; Pontoh, Julius; Fatimah, Feti

2016-01-01

Telah dilakukan penelitian mengenai penentuan batas deteksi (LOD) dan respon faktor (RF) GC Shimadzhu-2014 terhadap beberapa senyawa metil ester asam lemak (FAME). Adapun kajian yang dilakukan meliputi pembuatan dan pengenceran larutan FAME standard serta analisis dengan GC sebanyak 2 kali pengulangan sehingga didapat kurva standar senyawa FAME. Berdasarkan hasil analisis dengan GC, kurva standar masing-masing senyawa FAME memiliki presisi yang cukup baik yakni berkisar antara 0.995-0.999. Pe...

Resonance enhanced laser mass spectrometry for process- and environmental-analysis: Applications and perspectives

International Nuclear Information System (INIS)

Zimmermann, Ralf; Dorfner, Ralph; Kettrup, Antonius; Heger, Hans Joerg; Boesl, Ulrich

1998-01-01

Laser induced Resonance-Enhanced Multi-Photon Ionization Time-Of-Flight Mass Spectrometry (REMPI TOFMS) is a highly selective as well as sensitive analytical technique, well suited for species selective, on-line monitoring of trace-substances. In this contribution some analytical applications of a mobile REMPI-TOFMS are presented. This includes REMPI-TOMS on-line analysis of coffee roasting gas and waste incineration flue gas as well as headspace measurements of pulp processing lye or rapid analysis of polycyclic aromatic hydrocarbons from soil samples via thermal desorption

Qualitative and quantitative analysis on aroma characteristics of ginseng at different ages using E-nose and GC-MS combined with chemometrics.

Science.gov (United States)

Cui, Shaoqing; Wang, Jun; Yang, Liangcheng; Wu, Jianfeng; Wang, Xinlei

2015-01-01

Aroma profiles of ginseng samples at different ages were investigated using electronic nose (E-nose) and GC-MS techniques combined with chemometrics analysis. The bioactive ginsenoside and volatile oil content increased with age. E-nose performed well in the qualitative analyses. Both Principal Component Analysis (PCA) and Discriminant Functions Analysis (DFA) performed well when used to analyze ginseng samples, with the first two principal components (PCs) explaining 85.51% and the first two factors explaining 95.51% of the variations. Hierarchical Cluster Analysis (HCA) successfully clustered the different types of ginsengs into four groups. A total of 91 volatile constituents were identified. 50 of them were calculated and compared using GC-MS. The main fragrance ingredients were terpenes and alcohols, followed by aromatics and ester. The changes in terpenes, alcohols, aromatics, esters, and acids during the growth year once again confirmed the dominant role of terpenes. The Partial Least Squares (PLS) loading plot of gas sensors and aroma ingredients indicated that particular sensors were closely related to terpenes. The scores plot indicated that terpenes and its corresponding sensors contributed the most in grouping. As regards to quantitative analyze, 7 constituent of terpenes could be accurately explained and predicted by using gas sensors in PLS models. In predicting ginseng age using Back Propagation-Artificial Neural Networks (BP-ANN), E-nose data was found to predict more accurately than GC-MS data. E-nose measurement may be a potential method for determining ginseng age. The combination of GC-MS can help explain the hidden correlation between sensors and fragrance ingredients from two different viewpoints. Copyright © 2014 Elsevier B.V. All rights reserved.

Immunotherapy of metastatic breast cancer patients with vitamin D-binding protein-derived macrophage activating factor (GcMAF).

Science.gov (United States)

Yamamoto, Nobuto; Suyama, Hirofumi; Yamamoto, Nobuyuki; Ushijima, Naofumi

2008-01-15

Serum vitamin D3-binding protein (Gc protein) is the precursor for the principal macrophage activating factor (MAF). The MAF precursor activity of serum Gc protein of breast cancer patients was lost or reduced because Gc protein was deglycosylated by serum alpha-N-acetylgalactosaminidase (Nagalase) secreted from cancerous cells. Patient serum Nagalase activity is proportional to tumor burden. The deglycosylated Gc protein cannot be converted to MAF, resulting in no macrophage activation and immunosuppression. Stepwise incubation of purified Gc protein with immobilized beta-galactosidase and sialidase generated probably the most potent macrophage activating factor (termed GcMAF) ever discovered, which produces no adverse effect in humans. Macrophages treated in vitro with GcMAF (100 pg/ml) are highly tumoricidal to mammary adenocarcinomas. Efficacy of GcMAF for treatment of metastatic breast cancer was investigated with 16 nonanemic patients who received weekly administration of GcMAF (100 ng). As GcMAF therapy progresses, the MAF precursor activity of patient Gc protein increased with a concomitant decrease in serum Nagalase. Because of proportionality of serum Nagalase activity to tumor burden, the time course progress of GcMAF therapy was assessed by serum Nagalase activity as a prognostic index. These patients had the initial Nagalase activities ranging from 2.32 to 6.28 nmole/min/mg protein. After about 16-22 administrations (approximately 3.5-5 months) of GcMAF, these patients had insignificantly low serum enzyme levels equivalent to healthy control enzyme levels, ranging from 0.38 to 0.63 nmole/min/mg protein, indicating eradication of the tumors. This therapeutic procedure resulted in no recurrence for more than 4 years. Copyright 2007 Wiley-Liss, Inc.

Characterization of microbial metabolism of Syrah grape products in an in vitro colon model using targeted and non-targeted analytical approaches.

Science.gov (United States)

Aura, Anna-Marja; Mattila, Ismo; Hyötyläinen, Tuulia; Gopalacharyulu, Peddinti; Cheynier, Veronique; Souquet, Jean-Marc; Bes, Magali; Le Bourvellec, Carine; Guyot, Sylvain; Orešič, Matej

2013-03-01

Syrah red grapes are used in the production of tannin-rich red wines. Tannins are high molecular weight molecules, proanthocyanidins (PAs), and poorly absorbed in the upper intestine. In this study, gut microbial metabolism of Syrah grape phenolic compounds was investigated. Syrah grape pericarp was subjected to an enzymatic in vitro digestion model, and red wine and grape skin PA fraction were prepared. Microbial conversion was screened using an in vitro colon model with faecal microbiota, by measurement of short-chain fatty acids by gas chromatography (GC) and microbial phenolic metabolites using GC with mass detection (GC-MS). Red wine metabolites were further profiled using two-dimensional GC mass spectrometry (GCxGC-TOFMS). In addition, the effect of PA structure and dose on conversion efficiency was investigated by GC-MS. Red wine exhibited a higher degree of C1-C3 phenolic acid formation than PA fraction or grape pericarp powders. Hydroxyphenyl valeric acid (flavanols and PAs as precursors) and 3,5-dimethoxy-4-hydroxybenzoic acid (anthocyanin as a precursor) were identified from the red wine metabolite profile. In the absence of native grape pericarp or red wine matrix, the isolated PAs were found to be effective in the dose-dependent inhibition of microbial conversions and short-chain fatty acid formation. Metabolite profiling was complementary to targeted analysis. The identified metabolites had biological relevance, because the structures of the metabolites resembled fragments of their grape phenolic precursors or were in agreement with literature data.

Characterization of the volatile components in green tea by IRAE-HS-SPME/GC-MS combined with multivariate analysis.

Science.gov (United States)

Yang, Yan-Qin; Yin, Hong-Xu; Yuan, Hai-Bo; Jiang, Yong-Wen; Dong, Chun-Wang; Deng, Yu-Liang

2018-01-01

In the present work, a novel infrared-assisted extraction coupled to headspace solid-phase microextraction (IRAE-HS-SPME) followed by gas chromatography-mass spectrometry (GC-MS) was developed for rapid determination of the volatile components in green tea. The extraction parameters such as fiber type, sample amount, infrared power, extraction time, and infrared lamp distance were optimized by orthogonal experimental design. Under optimum conditions, a total of 82 volatile compounds in 21 green tea samples from different geographical origins were identified. Compared with classical water-bath heating, the proposed technique has remarkable advantages of considerably reducing the analytical time and high efficiency. In addition, an effective classification of green teas based on their volatile profiles was achieved by partial least square-discriminant analysis (PLS-DA) and hierarchical clustering analysis (HCA). Furthermore, the application of a dual criterion based on the variable importance in the projection (VIP) values of the PLS-DA models and on the category from one-way univariate analysis (ANOVA) allowed the identification of 12 potential volatile markers, which were considered to make the most important contribution to the discrimination of the samples. The results suggest that IRAE-HS-SPME/GC-MS technique combined with multivariate analysis offers a valuable tool to assess geographical traceability of different tea varieties.

Characterization of the volatile components in green tea by IRAE-HS-SPME/GC-MS combined with multivariate analysis.

Directory of Open Access Journals (Sweden)

Yan-Qin Yang

Full Text Available In the present work, a novel infrared-assisted extraction coupled to headspace solid-phase microextraction (IRAE-HS-SPME followed by gas chromatography-mass spectrometry (GC-MS was developed for rapid determination of the volatile components in green tea. The extraction parameters such as fiber type, sample amount, infrared power, extraction time, and infrared lamp distance were optimized by orthogonal experimental design. Under optimum conditions, a total of 82 volatile compounds in 21 green tea samples from different geographical origins were identified. Compared with classical water-bath heating, the proposed technique has remarkable advantages of considerably reducing the analytical time and high efficiency. In addition, an effective classification of green teas based on their volatile profiles was achieved by partial least square-discriminant analysis (PLS-DA and hierarchical clustering analysis (HCA. Furthermore, the application of a dual criterion based on the variable importance in the projection (VIP values of the PLS-DA models and on the category from one-way univariate analysis (ANOVA allowed the identification of 12 potential volatile markers, which were considered to make the most important contribution to the discrimination of the samples. The results suggest that IRAE-HS-SPME/GC-MS technique combined with multivariate analysis offers a valuable tool to assess geographical traceability of different tea varieties.

Urinary Amino Acid Analysis: A Comparison of iTRAQ®-LC-MS/MS, GC-MS, and Amino Acid Analyzer

Science.gov (United States)

Kaspar, Hannelore; Dettmer, Katja; Chan, Queenie; Daniels, Scott; Nimkar, Subodh; Daviglus, Martha L.; Stamler, Jeremiah; Elliott, Paul; Oefner, Peter J.

2009-01-01

Urinary amino acid analysis is typically done by cation-exchange chromatography followed by post-column derivatization with ninhydrin and UV detection. This method lacks throughput and specificity. Two recently introduced stable isotope ratio mass spectrometric methods promise to overcome those shortcomings. Using two blinded sets of urine replicates and a certified amino acid standard, we compared the precision and accuracy of gas chromatography/mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) of propyl chloroformate and iTRAQ® derivatized amino acids, respectively, to conventional amino acid analysis. The GC-MS method builds on the direct derivatization of amino acids in diluted urine with propyl chloroformate, GC separation and mass spectrometric quantification of derivatives using stable isotope labeled standards. The LC-MS/MS method requires prior urinary protein precipitation followed by labeling of urinary and standard amino acids with iTRAQ® tags containing different cleavable reporter ions distinguishable by MS/MS fragmentation. Means and standard deviations of percent technical error (%TE) computed for 20 amino acids determined by amino acid analyzer, GC-MS, and iTRAQ®-LC-MS/MS analyses of 33 duplicate and triplicate urine specimens were 7.27±5.22, 21.18±10.94, and 18.34±14.67, respectively. Corresponding values for 13 amino acids determined in a second batch of 144 urine specimens measured in duplicate or triplicate were 8.39±5.35, 6.23±3.84, and 35.37±29.42. Both GC-MS and iTRAQ®-LC-MS/MS are suited for high-throughput amino acid analysis, with the former offering at present higher reproducibility and completely automated sample pretreatment, while the latter covers more amino acids and related amines. PMID:19481989

Preparation of WO3/g-C3N4 composites and their application in oxidative desulfurization

Science.gov (United States)

Zhao, Rongxiang; Li, Xiuping; Su, Jianxun; Gao, Xiaohan

2017-01-01

WO3/graphitic carbon nitride (g-C3N4) composites were successfully synthesized through direct calcining of a mixture of WO3 and g-C3N4 at 400 °C for 2 h. The WO3 was prepared by calcination of phosphotungstic acid at 550 °C for 4 h, and the g-C3N4 was obtained by calcination of melamine at 520 °C for 4 h. The WO3/g-C3N4 composites were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), and Brunner-Emmett-Teller analysis (BET). The WO3/g-C3N4 composites exhibited stronger XRD peaks of WO3 and g-C3N4 than the WO3 and pure g-C3N4. In addition, two WO3 peaks at 25.7° and 26.6° emerged for the 36% -WO3/g-C3N4 composite. This finding indicated that WO3 was highly dispersed on the surface of the g-C3N4 nanosheets and interacted with the nanosheets, which resulted in the appearance of (012) and (022) planes of WO3. The WO3/g-C3N4 composite also exhibited a larger specific surface area and higher degree of crystallization than WO3 or pure g-C3N4, which resulted in high catalytic activity of the catalyst. Desulfurization experiments demonstrated that the desulfurization rate of dibenzothiophene (DBT) in model oil reached 91.2% under optimal conditions. Moreover, the activity of the catalyst was not significantly decreased after five recycles.

Identification and measurement of pesticide contaminants in food products by electron impact GC/MS

International Nuclear Information System (INIS)

Tusa, Florina; Moldovan, Zaharie; Vlassa, Mircea

2009-01-01

The paper concern is determination of eight pesticides in food products samples. The target compounds are: Lindane, Heptachlor, Aldrin, o,p-DDE, Dieldrin, Endrin, p,p'-DDT, and Methoxychlor. The compounds quantities were performed from chromatographic area obtained in full scan GC/MS mode after baseline separation and by comparation with surrogate internal standard area (Diphenylamine). The samples were concentrated by extraction with organic solvents (acetone) by Solid-Liquid Extraction (SLE) procedures the recovery factors being better than 80% except for Heptachlors. The coefficient of correlation of detector response function was better than 0.913 and LOQ under 0.015 μg/g. The method enables to determine pesticides at low μg/g in food supplements.

Analysis of acrylamide by LC-MS/MS and GC-MS in processed Japanese foods.

Science.gov (United States)

Ono, H; Chuda, Y; Ohnishi-Kameyama, M; Yada, H; Ishizaka, M; Kobayashi, H; Yoshida, M

2003-03-01

Acrylamide concentrations in processed foods (63 samples covering 31 product types) from Japan were analysed by LC-MS/MS and GC-MS methods. The limit of detection and limit of quantification of acrylamide were 0.2 ng x ml(-1) (6 fmol) and 0.8 ng x ml(-1) (22 fmol), respectively, by LC-MS/MS, and those of 2,3-dibromopropionamide derived from acrylamide were 12 ng x ml(-1) (52 fmol) and 40 ng x ml(-1) (170 fmol), respectively, by GC-MS. Repeatability given as RSD was 1000 microg x kg(-1). The concentrations in non-whole potato-based snacks, rice crackers processed by grilling or frying, and candied sweet potatoes were lower compared with those in the potato crisps and the whole potato-based fried snacks. One of the whole potato-based fried snacks, however, showed low acrylamide concentration (instant precooked noodles and won-tons were <100 microg x kg(-1) with only one exception. Roasted barley grains for 'Mugi-cha' tea contained 200-600 microg x kg(-1) acrylamide.

Gas chromatography/isotope ratio mass spectrometry: analysis of methanol, ethanol and acetic acid by direct injection of aqueous alcoholic and acetic acid samples.

Science.gov (United States)

Ai, Guomin; Sun, Tong; Dong, Xiuzhu

2014-08-15

Methanol, ethanol, and acetic acid are not easily extracted from aqueous samples and are susceptible to isotope fractionation in gas chromatography/isotope ratio mass spectrometry (GC/IRMS) analysis. Developing a direct dilution GC/IRMS method for aqueous samples, by adjusting the sample concentrations in common solvents to be similar to each other and using a fixed GC split ratio, is very convenient and important because any linearity effects caused by amount-dependent isotope fractionation can be avoided. The suitability of acetonitrile and acetone solvents for the GC/IRMS analysis of pure methanol, ethanol and acetic acid, and commercial liquor and vinegar samples was evaluated using n-hexane and water as control solvents. All the solvents including water were separated from the analyte on a HP-INNOWAX column and were diverted away from the combustion interface. The influence of liquor matrix on the ethanol GC/IRMS analyses was evaluated by adding pure ethanol to liquor samples. Acetonitrile and acetone gave similar δ(13) C values for pure ethanol and pure acetic acid to those obtained in water and n-hexane, and also gave similar δ(13) C values of ethanol in liquor and acetic acid in white vinegar to that obtained in water. For methanol analysis, acetonitrile and refined acetone gave similar δ(13) C values to that obtained in water, but n-hexane was not a suitable solvent. In addition, isotopic fractionation caused by solvent and solute interactions was observed. We recommend using acetonitrile for the GC/IRMS analysis of aqueous alcoholic samples, and acetone for the analysis of aqueous acetic acid samples. This direct dilution method can provide high accurate and precise GC/IRMS analysis of the relative changes in δ(13) C values of methanol, ethanol, and acetic acid. Copyright © 2014 John Wiley & Sons, Ltd.