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Sample records for chromatographic-mass spectrometric method

  1. Validation of a simple gas chromatographic-mass spectrometric method for the determination of gamma-butyrolactone in human plasma.

    Science.gov (United States)

    Fukui, Yousuke; Matsusima, Eiji; Muramoto, Kouichi; Nagai, Nobutaka; Ohama, Koso; Yamashita, Kazumasa

    2003-02-25

    A gas chromatographic-mass spectrometric (GC-MS) method is described for the determination of human plasma levels of gamma-butyrolactone (GBL) is described. The method is sensitive and simple. The plasma sample spiked with the internal standard was extracted by dichloromethane (CH(2)Cl(2)) in acidic conditions, and the concentrated organic layer was injected into GC-MS. Because of endogenous GBL in human plasma, the method used a standard calibration curve. The calibration curve was linear from 10 to 1000 ng/ml. The method has been validated for accuracy and precision with the relative error and C.V. for intra- and inter-day within 10%. GBL-spiked plasma samples stored at -80 degrees C were stable for a 3-month period. The stability of plasma samples after three cycles of freezing and thawing and of prepared samples on an autosampler for 48 h were demonstrated. Plasma concentrations of GBL before and after administration of UFT were 24.3+/-14.2 and 84.9+/-22.4 ng/ml, respectively.

  2. Development of a gas chromatographic/mass spectrometric method for determination of phthalates in oily foods.

    Science.gov (United States)

    Sannino, Anna

    2010-01-01

    A GC/MS method was developed for simultaneous determination of 12 phthalates and four other plasticizers--acetyl tributyl citrate, di(2-ethylhexyl) adipate, dibutyl sebacate, di-isononyl cyclohexane 1,2-dicarboxylate (DINCH)--in vegetable oil, pesto, and tomato sauce. Samples were extracted with acetonitrile and cleaned on a Florisil column. The final extract was analyzed by GC in combination with ion trap MS. The phthalates and di-isononyl cyclohexane 1,2-dicarboxylate were detected by MS/MS, while the other three plasticizers were monitored in the same GC run using full scan mode. The analytical process was validated in each matrix by the analysis of blank samples. Performance characteristics, such as linearity, LOQ, precision, and recoveries were studied. Studies at fortification levels of 0.25-200 mg/kg gave mean recoveries ranging from 71 to 106% and RSD values between 7 and 12% for all compounds. LOQs were 0.050-0.10 mg/kg for all the target compounds except di-isononyl phthalate, di-isodecyl phthalate, and DINCH (2.0 mg/kg).

  3. A gas/liquid chromatographic-mass spectrometric method for the rapid screening of 250 pesticides in aqueous matrices

    Energy Technology Data Exchange (ETDEWEB)

    Chandramouli, B.; Harvan, D.; Brittain, S.; Hass, R. [Eno River Labs, LLC. Durham, NC (United States)

    2004-09-15

    Pesticide residues in food present a potentially serious and significant cause for concern. Many pesticides have been associated with significant health effects to the nervous and endocrine systems and some have been deemed carcinogenic. There are many well-established techniques for pesticide analysis. However, commercial pesticide methods have traditionally only been available for specific pesticide families, such as chlorinated pesticides or herbicides, and at detection limits ranging from 0.05 ppb to 1 ppm in aqueous matrices. Techniques that can quickly screen for the presence/absence of pesticide residues in food matrices are critical in ensuring the safety of food and water. This paper outlines a combined Gas Chromatographic-High Resolution Mass Spectrometric (GC-HRMS) and Liquid Chromatographic Tandem Mass Spectrometric (LC-MS/MS) screening assay for 250 pesticides that was developed for use in water, and soda samples at screening levels ranging from 0.1-5 ppb. The pesticides selected have been identified by the European Union as being of concern and the target of possible legislation. The list encompasses a variety of pesticide classes and compound groupings.

  4. Liquid chromatographic-mass spectrometric analysis of glucuronide-conjugated anabolic steroid metabolites: method validation and interlaboratory comparison

    NARCIS (Netherlands)

    Hintikka, L.; Kuuranne, T.; Leinonen, A.; Thevis, M.; Schanzer, W.; Halket, J.; Cowan, D.; Grosse, J.; Hemmersbach, P.; Nielen, M.W.F.; Kostiainen, R.

    2008-01-01

    Liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) method for simultaneous and direct detection of 12 glucuronide-conjugated anabolic androgenic steroid (AAS) metabolites in human urine is described. The compounds selected were the main metabolites detected in huma

  5. Gas Chromatographic Mass Spectrometric Determination of Myo-inositol in Humans Utilizing a Deuterated Internal Standard

    DEFF Research Database (Denmark)

    Andersen, Jan Rud; Larsen, Elfinn; Harbo, Helge;

    1982-01-01

    , was added as internal standard to the samples at an early stage in the analytical procedure. After separation and derivatization to the hexa-acetate, the gas chromatographic mass spectrometric analysis was carried out. A 25 m fused silica capillary column coated with methyl silicone was used, and the ions...

  6. A sensitive liquid chromatographic-mass spectrometric method for simultaneous quantification of six iridoid glycosides from Zhi-zi-chi Decoction in rat plasma and its application to a pharmacokinetic study.

    Science.gov (United States)

    Qu, Kankan; Dai, Jinna; Zhao, Longshan; Lu, Yanan; Li, Bin; Zhao, Xu; Hou, Pengyi; Zhang, Yuanting; Bi, Kaishun; Chen, Xiaohui

    2013-05-01

    A sensitive liquid chromatographic-mass spectrometric (LC-MS) method was developed and validated for simultaneous determination of geniposide, geniposidic acid, scandoside methyl ester, gardenoside, deacetyl asperulosidic acid methyl ester and genipin-1-β-gentiobioside after oral administration of Zhi-zi-chi Decoction in rat plasma. The six iridoid glycosides were extracted from plasma samples by protein precipitation, and then separated on an Apollo C18 column (250 mm × 4.6mm, 5 μm) through the application of a gradient elution. The analytes were monitored in positive electrospray ionization by selected ion monitoring mode (SIM). The lower limits of quantitation (LLOQ) of the six analytes were all lower than 6 ng/mL. The accuracy (relative error, RE%) was between -7.0% and 9.9%, while the intra- and inter-day precisions (relative standard deviation, RSD%) were less than 6.3% and 9.8% for the six analytes, respectively. The developed method was successfully applied to a comparative pharmacokinetic study of the six iridoids in rat plasma after oral administration of Zhi-zi-chi Decoction and Gardenia jasminoides extract.

  7. QuEChERS Method Followed by Solid Phase Extraction Method for Gas Chromatographic-Mass Spectrometric Determination of Polycyclic Aromatic Hydrocarbons in Fish

    Directory of Open Access Journals (Sweden)

    Mona Khorshid

    2015-01-01

    Full Text Available A gas chromatography equipped with mass spectrometer (GCMS method was developed and validated for determination of 16 polycyclic aromatic hydrocarbons (PAHs in fish using modified quick, easy, cheap, effective, rugged, and safe (QuEChERS method for extraction and solid phase extraction for sample cleanup to remove most of the coextract combined with GCMS for determination of low concentration of selected group of PAHs in homogenized fish samples. PAHs were separated on a GCMS with HP-5ms Ultra Inert GC Column (30 m, 0.25 mm, and 0.25 µm. Mean recovery ranged from 56 to 115%. The extraction efficiency was consistent over the entire range where indeno(1,2,3-cdpyrene and benzo(g,h,iperylene showed recovery (65, 69%, respectively, at 2 µg/kg. No significant dispersion of results was observed for the other remaining PAHs and recovery did not differ substantially, and at the lowest and the highest concentrations mean recovery and RSD% showed that most of PAHs were between 70% and 120% with RSD less than 10%. The measurement uncertainty is expressed as expanded uncertainty and in terms of relative standard deviation (at 95% confidence level is ±12%. This method is suitable for laboratories engaged daily in routine analysis of a large number of samples.

  8. A quantitative structure- property relationship of gas chromatographic/mass spectrometric retention data of 85 volatile organic compounds as air pollutant materials by multivariate methods

    Directory of Open Access Journals (Sweden)

    Sarkhosh Maryam

    2012-05-01

    Full Text Available Abstract A quantitative structure-property relationship (QSPR study is suggested for the prediction of retention times of volatile organic compounds. Various kinds of molecular descriptors were calculated to represent the molecular structure of compounds. Modeling of retention times of these compounds as a function of the theoretically derived descriptors was established by multiple linear regression (MLR and artificial neural network (ANN. The stepwise regression was used for the selection of the variables which gives the best-fitted models. After variable selection ANN, MLR methods were used with leave-one-out cross validation for building the regression models. The prediction results are in very good agreement with the experimental values. MLR as the linear regression method shows good ability in the prediction of the retention times of the prediction set. This provided a new and effective method for predicting the chromatography retention index for the volatile organic compounds.

  9. A strategy for the systematic development of a liquid chromatographic mass spectrometric screening method for polymer electrolyte membrane degradation products using isocratic and gradient phase optimized liquid chromatography.

    Science.gov (United States)

    Zedda, M; Tuerk, J; Teutenberg, T; Peil, S; Schmidt, T C

    2009-12-18

    Within the scope of research for target and non-target LC-MS/MS analysis of membrane degradation products of polymer electrolyte membrane fuel cells, a systematic method development for the separation of structurally similar compounds was performed by phase optimized liquid chromatography. Five different stationary phases with different selectivities were used. Isocratic separation for 4-hydroxybenzoic acid, isophthalic acid, terephthalic acid, 4-hydroxybenzaldehyde and 4-formylbenzoic acid was achieved on a C18 and a Phenyl phase. Using the PRISMA model the separation efficiency was optimized. This was achieved on a serially connected mixed stationary phase composed of 30 mm C18, 150 mm Phenyl and 60 mm C30. For the LC-MS screening of unknown degradation products from polymer electrolyte membranes in the product water of a fuel cell, a solvent gradient is mandatory for less polar or later eluting compounds. By means of 4-mercaptobenzoic acid it could be shown that a solvent gradient can be applied in order to elute later eluting compounds in a short time. The adaptability of this method for the qualitative analysis by target and non-target LC-MS/MS screening has been shown by means of 4-hydroxybenzoic acid. The combination of solvent gradient and isocratic conditions makes this approach attractive for the purpose of a screening method for known and unknown analytes in a water sample.

  10. Application of headspace sorptive extraction and gas chromatographic/mass spectrometric and chemometric methods to the quantification of pine nuts and pecorino in Pesto Genovese.

    Science.gov (United States)

    Zunin, Paola; Leardi, Riccardo; Boggia, Raffaella

    2009-01-01

    Headspace sorptive extraction and GC/MS, coupled with chemometric tools, were used to predict the amounts of pine nuts and Pecorino in Pesto Genovese, a typical Italian basil-based pasta sauce. Two groups of samples were prepared at different times and with ingredients from different batches for building the predicting models and testing their performances. Principal component analysis and partial least-squares regression (PLS) were applied to the chromatographic data. The 24 most-predictive variables were selected, and the application of PLS to the training set samples led to two models that explained approximately 70% of the variance in cross-validation, with prediction errors of 0.1 g for Pecorino and 0.6 g for pine nuts, thus confirming the reliability of the analytical method and the predicting ability of the models. The results obtained for the test set samples were not completely satisfactory, with a prediction error and a bias of 5.0 and -4.1 g, respectively, for Pecorino and corresponding values of 4.1 and 2.0 g for pine nuts. This preliminary study shows that the analytical methods used can allow construction of models with high predictive ability only if the great variability of the headspace composition of the ingredients and the effect of Twister are considered.

  11. Determination of two mebeverine metabolites, mebeverine alcohol and desmethylmebeverine alcohol, in human plasma by a dual stable isotope-based gas chromatographic-mass spectrometric method.

    Science.gov (United States)

    Tulich, L J; Randall, J L; Kelm, G R; Wehmeyer, K R

    1996-07-12

    A dual stable isotope-based GC-MS method was developed for the simultaneous determination of two metabolites of mebeverine, mebeverine alcohol and desmethylmebeverine alcohol, in human plasma. Plasma samples were treated with beta-glucuronidase to cleave the glucuronide conjugates of both compounds prior to analysis. The treated plasma was prepared for analysis by solid-phase extraction using octadecylsilane cartridges. The isolated metabolites were derivatized and analyzed by GC-MS using selected-ion monitoring. Plots of peak-area ratio were linear with metabolite concentration from 2 to 200 ng/ml and the limit of detection for both metabolites was 0.5 ng/ml. The GC-MS methodology was applied to the analysis of plasma from human subjects following peroral administration of mebeverine. Pharmacokinetic parameters for both metabolites were determined and suggest that relative systemic mebeverine exposure may potentially be assessed using metabolite kinetics, if the latter subsequently are demonstrated to be linear with mebeverine dose.

  12. Comparison of solid-phase microextraction and dynamic headspace methods for the gas chromatographic-mass spectrometric analysis of light-induced lipid oxidation products in milk.

    Science.gov (United States)

    Marsili, R T

    1999-01-01

    A sensitive, rapid procedure for testing lipid oxidation products in milk is developed using solid-phase microextraction (SPME) and gas chromatography-mass spectrometry. SPME is as sensitive as dynamic headspace (DH) analysis for measuring the pentanal and hexanal produced in milk after exposure to light. Furthermore, compared with DH, SPME is less expensive and demonstrates better precision and accuracy. In addition, SPME does not exhibit carryover or septa artifact peaks. The linearity of calibration curves (based on the method of additions technique with an internal standard) is consistently better for SPME than for DH. Furthermore, replicate analyses of pentanal and hexanal spiked in skim milk and 2% milk at 2 ng/mL demonstrate significantly lower coefficients of variation using SPME. To further test the practicality of SPME for measuring light-induced chemical changes in milk, 2% milk and skim milk samples are exposed to fluorescent light (200 foot-candles) for 0, 3, 6, 9, 12, 17, 24, and 48 h and analyzed by SPME and DH. Pentanal and hexanal in all samples are measured by SPME and DH. Correlation coefficients of resulting plots indicate that SPME is more accurate than DH in measuring the quantity of lipid oxidation products in milk.

  13. Gas chromatographic-mass spectrometric analysis of steroids and steroid glucuronides in the seminal vesicle fluid of the African catfish, Clarias gariepinus

    NARCIS (Netherlands)

    Schoonen, W.G.E.J.; Lambert, J.G.D.

    1987-01-01

    Gas chromatographic-mass spectrometric analysis was carried out to identify steroids and steroid glucuronides in the seminal vesicle fluid of African catfish, Clarias gariepinus, collected in the Hula nature reserve (Israel) during the breeding season. Full mass spectra of 5β-pregnane-3α,17α-diol-20

  14. Rapid screening of phytosterols in orange juice by solid-phase microextraction on polyacrylate fibre derivatisation and gas chromatographic-mass spectrometric.

    Science.gov (United States)

    Balme, Sébastien; Gülaçar, Fazil O

    2012-05-01

    The potential of solid-phase microextraction on polyacrylate coated fibre, with sequential or simultaneous trimethylsilyl derivatisation followed by gas chromatographic-mass spectrometric analysis, was evaluated for a rapid determination of the distribution of the phytosterols in aqueous food matrixes. Influences of different parameters (bis(trimethylsilyl)trifluoro-acetamide and sterol exposure time, sterol concentration and experimental protocol) on the recovery of sterols were investigated to determine optimum conditions which were tested for sterol extraction and analysis from orange juice. Best selectivity, sterol recovery and derivatisation yields were obtained by extraction and simultaneous derivatisation through immersion of the SPME-PA fibre in the orange juice (10min, 65°C) after headspace absorption of BSTFA (30min, 65°C) on the fibre. Nevertheless the method developed cannot be used for quantitative analysis. But the possibility to effect rapid screen of phytosterol containing in complex media have been shown.

  15. Gas chromatographic/mass spectrometric determination of lysergic acid diethylamide (LSD) in serum samples.

    Science.gov (United States)

    Musshoff, F; Daldrup, T

    1997-08-04

    A sensitive method for the detection and quantification of lysergic acid diethylamide (LSD) in serum samples is described. After liquid-liquid extraction the trimethylsilyl derivative of LSD is detected by gas chromatography-mass spectrometry. Experiments with spiked samples resulted in a recovery of 76%, the coefficient of variation was 9.3%. Excellent linearity was obtained over the range 0.1-10 ng ml-1. Additionally experiments demonstrating the light sensitivity of LSD are presented together with casuistics.

  16. Gas chromatographic-mass spectrometric analysis of acrylamide and acetamide in cigarette mainstream smoke after on-column injection.

    Science.gov (United States)

    Diekmann, Joerg; Wittig, Arno; Stabbert, Regina

    2008-08-01

    A method is described for the simultaneous determination of two short-chained amides, acrylamide and acetamide (classified by the International Agency for Research on Cancer as probable and possible human carcinogens, respectively), in total particulate matter using gas chromatography-on-column injection and mass spectrometric detection. Sample preparation is kept to a minimum, and the proposed analytical procedure proves to be fast, sensitive, and precise. Validation studies show good linearity with a regression coefficient of r2=.000 for both compounds. Quantitation limits are 32 ng/mL for acrylamide and 70 ng/mL for acetamide. In the particulate phase of mainstream smoke from the University of Kentucky Reference Cigarette 2R4F, 2.3 microg/cig acrylamide and 4.7 microg/cig acetamide are found; no acetamide and only .0074 microg/cig acrylamide is found in the gas phase. Possible mechanisms of formation in cigarette smoke are discussed.

  17. A SURVEY OF LIQUID CHROMATOGRAPHIC-MASS SPECTROMETRIC ANALYSIS OF MERCAPTURIC ACID BIOMARKERS IN OCCUPATIONAL AND ENVIRONMENTAL EXPOSURE MONITORING

    Science.gov (United States)

    Mathias, Patricia I.; B’Hymer, Clayton

    2015-01-01

    High-performance liquid chromatography/mass spectrometry (HPLC/MS) is sensitive and specific for targeted quantitative analysis and is readily utilized for small molecules from biological matricies. This brief review describes recent selected HPLC/MS methods for the determination of urinary mercapturic acids (mercapturates) which are useful as biomarkers in characterizing human exposure to electrophilic industrial chemicals in occupational and environmental studies. Electrophilic compounds owing to their reactivity are used in chemical and industrial processes. They are present in industrial emissions, are combustion products of fossil fuels, and are components in tobacco smoke. Their presence in both the industrial and general environment are of concern for human and environmental health. Urinary mercapturates which are the products of metabolic detoxification of reactive chemicals provide a non-invasive tool to investigate human exposure to electrophilic toxicants. Selected recent mercapturate quantification methods are summarized and specific cases are presented. The biological formation of mercapturates is introduced and their use as biomarkers of metabolic processing of electrophilic compounds is discussed. Also, the use of liquid chromatography/tandem mass spectrometry in simultaneous determinations of the mercapturates of multiple parent compounds in a single determination is considered, as well as future trends and limitations in this area of research. PMID:24746702

  18. Gas chromatographic-mass spectrometric fragmentation study of phytoestrogens as their trimethylsilyl derivatives: Identification in soy milk and wastewater samples

    Science.gov (United States)

    Ferrer, I.; Barber, L.B.; Thurman, E.M.

    2009-01-01

    An analytical method for the identification of eight plant phytoestrogens (biochanin A, coumestrol, daidzein, equol, formononetin, glycitein, genistein and prunetin) in soy products and wastewater samples was developed using gas chromatography coupled with ion trap mass spectrometry (GC/MS-MS). The phytoestrogens were derivatized as their trimethylsilyl ethers with trimethylchlorosilane (TMCS) and N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA). The phytoestrogens were isolated from all samples with liquid-liquid extraction using ethyl acetate. Daidzein-d4 and genistein-d4 labeled standards were used as internal standards before extraction and derivatization. The fragmentation patterns of the phytoestrogens were investigated by isolating and fragmenting the precursor ions in the ion-trap and a typical fragmentation involved the loss of a methyl and a carbonyl group. Two characteristic fragment ions for each analyte were chosen for identification and confirmation. The developed methodology was applied to the identification and confirmation of phytoestrogens in soy milk, in wastewater effluent from a soy-milk processing plant, and in wastewater (influent and effluent) from a treatment plant. Detected concentrations of genistein ranged from 50,000 ??g/L and 2000 ??g/L in soy milk and in wastewater from a soy-plant, respectively, to 20 ??g/L and <1 ??g/L for influent and effluent from a wastewater treatment plant, respectively. ?? 2009 Elsevier B.V.

  19. Gas chromatographic-mass spectrometric characterization of all acyclic C5-C7 alkenes from fluid catalytic cracked gasoline using polydimethylsiloxane and squalane stationary phases.

    Science.gov (United States)

    Soják, Ladislav; Addová, Gabriela; Kubinec, Róbert; Kraus, Angelika; Hu, Gengyuan

    2002-02-15

    Published retention indices of acyclic alkenes C5-C7 on squalane and polydimethylsiloxane as stationary phases were investigated, and reliable retention indices of alkenes from various sources were converted to separation systems used in a laboratory. Retention indices measured on available authentic commercial alkenes and on alkenic fraction of gasoline, published retention indices as well as means of GC-MS were used for verification of calculated retention indices. Retention of some gas chromatographic unseparated isomer pairs was obtained by mass spectrometric deconvolution using a specific single-ion monitoring. On the basis of these retention data, C5-C7 alkenes were identified and analyzed in the gasoline from fluid catalytic cracking. In the gasoline all 59 acyclic C5-C7 isomeric alkenes were determined at significantly different concentration levels.

  20. A gas chromatograph/mass spectrometry method for determining isotopic distributions in organic compounds used in the chemical approach to stable isotope separation

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, A.M.; Spall, W.D.; Smith, B.F.

    1990-01-01

    A variety of gas chromatograph/mass spectrometry (GC/MS) methods have been developed to resolve benzene, benzophenone, anthracene, fluorenone, and their respective stable isotope analogs from other components by gas chromatography. The ratio of stable isotope-labeled material to natural isotopic abundance compounds is determined from the mass spectra averaged across the chromatographic peak. Both total ion and selective ion chromatographic approaches were used for relative data and comparison. 9 refs., 11 tabs.

  1. Comprehensive automation of the solid phase extraction gas chromatographic mass spectrometric analysis (SPE-GC/MS) of opioids, cocaine, and metabolites from serum and other matrices.

    Science.gov (United States)

    Lerch, Oliver; Temme, Oliver; Daldrup, Thomas

    2014-07-01

    The analysis of opioids, cocaine, and metabolites from blood serum is a routine task in forensic laboratories. Commonly, the employed methods include many manual or partly automated steps like protein precipitation, dilution, solid phase extraction, evaporation, and derivatization preceding a gas chromatography (GC)/mass spectrometry (MS) or liquid chromatography (LC)/MS analysis. In this study, a comprehensively automated method was developed from a validated, partly automated routine method. This was possible by replicating method parameters on the automated system. Only marginal optimization of parameters was necessary. The automation relying on an x-y-z robot after manual protein precipitation includes the solid phase extraction, evaporation of the eluate, derivatization (silylation with N-methyl-N-trimethylsilyltrifluoroacetamide, MSTFA), and injection into a GC/MS. A quantitative analysis of almost 170 authentic serum samples and more than 50 authentic samples of other matrices like urine, different tissues, and heart blood on cocaine, benzoylecgonine, methadone, morphine, codeine, 6-monoacetylmorphine, dihydrocodeine, and 7-aminoflunitrazepam was conducted with both methods proving that the analytical results are equivalent even near the limits of quantification (low ng/ml range). To our best knowledge, this application is the first one reported in the literature employing this sample preparation system.

  2. Gas Chromatographic-Mass Spectrometric Analysis of Volatiles Obtained by Four Different Techniques from Salvia rosifolia Sm. and Evaluation for Biological Activity

    Science.gov (United States)

    Volatile constituents from the aerial parts of Salvia rosifolia Sm. (Lamiaceae), endemic to Turkey, were obtained by four different isolation techniques and then analyzed by gas chromatography (GC/FID) and gas chromatography – mass spectrometry (GC/MS) methods. Also in scope of the present work, the...

  3. On-line study of flavonoids of Trollius chinensis Bunge binding to DNA with ethidium bromide using a novel combination of chromatographic, mass spectrometric and fluorescence techniques.

    Science.gov (United States)

    Song, Zhiling; Wang, Hong; Ren, Biao; Zhang, Baobao; Hashi, Yuki; Chen, Shizhong

    2013-03-22

    The study of the interaction between drugs and DNA is an important way to understand the role of drug molecules. A novel online analytical method for this purpose combining high-performance liquid chromatography-diode array detector-electrospray ionization-ion-trap time-of-flight mass spectrometry (HPLC-DAD-ESI-IT-TOF-MS(n)) and DNA-ethidium bromide detection with a fluorescence detector (DNA-EB-FLD) was firstly developed, which could rapidly identify the chemical constituents and obtain the profile related to DNA binding activity. This method has been applied for a precise or probable identification of the chemical constituents by ultraviolet (UV) absorption and MS(n) data analysis, while the DNA binding profile has been characterized by directly measuring the fluorescence intensity of compound-DNA-EB. Using this method, Trollius chinensis Bunge was studied and 18 constituents were identified by MS(n) data; six of them (4'-methoxy-2″-O-(2‴-methylbutyryl)vitexin,2″-O-(3‴-methoxycaffeoyl)vitexin) and 4'-methoxy-2″-O-(2‴-methylbutyryl)orientin,acacetin-7-O-rutinoside,quercetin-3-O-xylosylglucoside,quercetin-3-O-arabinosylglucoside) were identified for the first time in T. chinensis Bunge, and 16 constituents accounted for its activity of binding to DNA. The established (HPLC-DAD-ESI-IT-TOF-MS(n) DNA-EB-FLD) system has proved to offer a useful strategy for correlating the chemical profile with the binding to DNA activities of the components without their isolation and purification, and may be used for multicomponent analysis of active substances in other herbs.

  4. Monolithic silica spin column extraction and simultaneous derivatization of amphetamines and 3,4-methylenedioxyamphetamines in human urine for gas chromatographic-mass spectrometric detection.

    Science.gov (United States)

    Nakamoto, Akihiro; Nishida, Manami; Saito, Takeshi; Kishiyama, Izumi; Miyazaki, Shota; Murakami, Katsunori; Nagao, Masataka; Namura, Akira

    2010-02-19

    A simple, sensitive, and specific method with gas chromatography-mass spectrometry was developed for simultaneous extraction and derivatization of amphetamines (APs) and 3,4-methylenedioxyamphetamines (MDAs) in human urine by using a monolithic silica spin column. All the procedures, such as sample loading, washing, and elution were performed by centrifugation. APs and MDAs in urine were adsorbed on the monolithic silica and derivatized with propyl chloroformate in the column. Methamphetamine-d(5) was used as an internal standard. The linear ranges were 0.01-5.0 microg mL(-1) for methamphetamine (MA) and 3,4-methylenedioxymethamphetamine (MDMA) and 0.02-5.0 microg mL(-1) for amphetamine (AP) and 3,4-methylenedioxyamphetamine (MDA) (coefficient of correlation > or = 0.995). The recovery of APs and MDAs in urine was 84-94%, and the relative standard deviation of the intra- and interday reproducibility for urine samples containing 0.1, 1.0, and 4.0 microg mL(-1) of APs and MDAs ranged from 1.4% to 13.6%. The lowest detection limit (signal-to-noise ratio > or = 3) in urine was 5 ng mL(-1) for MA and MDMA and 10 ng mL(-1) for AP and MDA. The proposed method can be used to perform simultaneous extraction and derivatization on spin columns that have been loaded with a small quantity of solvent by using centrifugation.

  5. Monolithic silica spin column extraction and simultaneous derivatization of amphetamines and 3,4-methylenedioxyamphetamines in human urine for gas chromatographic-mass spectrometric detection

    Energy Technology Data Exchange (ETDEWEB)

    Nakamoto, Akihiro [Scientific Investigation Laboratory, Hiroshima Prefectural Police Headquarters, Kohnan 2-26-3, Naka-ku, Hiroshima 730-0825 (Japan); Nishida, Manami [Hiroshima University Technical Center, Kasumi 1-2-3, Minami-ku, Hiroshima 734-8551 (Japan); Saito, Takeshi [Department of Emergency and Critical Care Medicine, Tokai University School of Medicine, Shimokasuya 143, Isehara, Kanagawa 259-1143 (Japan); Kishiyama, Izumi; Miyazaki, Shota [GL Sciences Inc., Sayamagahara 237-2, Iruma, Saitama 358-0032 (Japan); Murakami, Katsunori [Scientific Investigation Laboratory, Hiroshima Prefectural Police Headquarters, Kohnan 2-26-3, Naka-ku, Hiroshima 730-0825 (Japan); Nagao, Masataka [Department of Forensic Medicine, Graduate School of Biomedical Sciences, Hiroshima University, Kasumi 1-2-3, Minami-ku, Hiroshima 734-8551 (Japan); Namura, Akira, E-mail: namera@hiroshima-u.ac.jp [Department of Forensic Medicine, Graduate School of Biomedical Sciences, Hiroshima University, Kasumi 1-2-3, Minami-ku, Hiroshima 734-8551 (Japan)

    2010-02-19

    A simple, sensitive, and specific method with gas chromatography-mass spectrometry was developed for simultaneous extraction and derivatization of amphetamines (APs) and 3,4-methylenedioxyamphetamines (MDAs) in human urine by using a monolithic silica spin column. All the procedures, such as sample loading, washing, and elution were performed by centrifugation. APs and MDAs in urine were adsorbed on the monolithic silica and derivatized with propyl chloroformate in the column. Methamphetamine-d{sub 5} was used as an internal standard. The linear ranges were 0.01-5.0 {mu}g mL{sup -1} for methamphetamine (MA) and 3,4-methylenedioxymethamphetamine (MDMA) and 0.02-5.0 {mu}g mL{sup -1} for amphetamine (AP) and 3,4-methylenedioxyamphetamine (MDA) (coefficient of correlation {>=}0.995). The recovery of APs and MDAs in urine was 84-94%, and the relative standard deviation of the intra- and interday reproducibility for urine samples containing 0.1, 1.0, and 4.0 {mu}g mL{sup -1} of APs and MDAs ranged from 1.4% to 13.6%. The lowest detection limit (signal-to-noise ratio {>=} 3) in urine was 5 ng mL{sup -1} for MA and MDMA and 10 ng mL{sup -1} for AP and MDA. The proposed method can be used to perform simultaneous extraction and derivatization on spin columns that have been loaded with a small quantity of solvent by using centrifugation.

  6. Analysis of Biologic Samples for Morphine and Morphine-Related Compounds by Gas Chromatographic-Mass Spectrometric Methods

    Science.gov (United States)

    1976-04-01

    included the synthesis of stable isotope labeled com- pounds and derivatives of morphine and morphine-related compounds, and the development of analytical...formation is not necessary if the purpose is to detect diacetylinorphine or methadone but most screening procedures have as their purpose the detection of a... Synthesis of reference compounds S•1 . Acyl derivatives Acetyl derivatives of alcohols or phenols are best prepared by reaction with acetic anhydride

  7. New Imaging Spectrometric Method for Rotary Object

    Institute of Scientific and Technical Information of China (English)

    方俊永; 赵达尊; 蒋月娟; 楚建军

    2003-01-01

    A new technique for imaging spectrometer for rotary object based on computed-tomography is proposed. A discrete model of this imaging spectrometric system is established, which is accordant to actual measurements and convenient for computation. In computer simulations with this method, projections of the object are detected by CCD while the object is rotating, and the original spectral images are numerically reconstructed from them by using the algorithm of computed-tomography. Simulation results indicate that the principle of the method is correct and it performs well for both broadband and narrow-band spectral objects.

  8. Optimized determination of trace jet fuel volatile organic compounds in human blood using in-field liquid-liquid extraction with subsequent laboratory gas chromatographic-mass spectrometric analysis and on-column large-volume injection.

    Science.gov (United States)

    Liu, S; Pleil, J D

    2001-03-05

    A practical and sensitive method to assess volatile organic compounds (VOCs) from JP-8 jet fuel in human whole blood was developed by modifying previously established liquid-liquid extraction procedures, optimizing extraction times, solvent volume, specific sample processing techniques, and a new on-column large-volume injection method for GC-MS analysis. With the optimized methods, the extraction efficiency was improved by 4.3 to 20.1 times and the detection sensitivity increased up to 660 times over the standard method. Typical detection limits in the parts-per-trillion (ppt) level range were achieved for all monitored JP-8 constituents; this is sufficient for assessing human fuels exposures at trace environmental levels as well as occupational exposure levels. The sample extractions are performed in the field and only solvent extracts need to be shipped to the laboratory. The method is implemented with standard biological laboratory equipment and a modest bench-top GC-MS system.

  9. Development and validation of a high performance liquid chromatographic-mass spectrometry method for the simultaneous quantification of 10 trichothecenes in ultra-high temperature processed cow milk.

    Science.gov (United States)

    Flores-Flores, Myra E; González-Peñas, Elena

    2015-11-06

    An LC-MS/MS (QqQ) method has been developed and validated for simultaneous determination of the following trichothecenes in UHT cow milk: nivalenol (NIV), deoxynivalenol (DON), deepoxy-deoxynivalenol (DOM-1), 3-acetyldeoxynivalenol (3-ADON), 15-acetyldeoxynivalenol (15-ADON), neosolaniol (NEO), diacetoxyscirpenol (DAS), fusarenon X (FUS-X), T-2 and HT-2 toxins. Sample treatment is simple and based on the extraction with acetonitrile (ACN), acidified with 0.2% formic acid, followed by a purification process, adding sodium acetate to the ACN/water extract in order to separate aqueous phase and, consequently, polar components of the milk. Validation of the method for all the 10 mycotoxins was successful; validation parameters taken into account were as follows: limits of detection (LOD) and quantification (LOQ), linearity, precision (within-day and between-day variability), recovery, matrix effect and stability. The LODs were 10.1, 2.5, 1.5, 1.9, 0.1, 0.5, 1.0, 0.08, 0.4 and 0.05ng/mL for NIV, DON, DOM-1, FUS-X, NEO, 3-ADON, 15-ADON, DAS, HT-2 and T-2, respectively. Mean recovery values (obtained in intermediate precision conditions) were between 63.5 and 75.8 (RSDR≤15%) for all the mycotoxins. All the mycotoxins suffered from matrix effects, especially DON.

  10. Extraction, chromatographic and mass spectrometric methods for lipid analysis.

    Science.gov (United States)

    Pati, Sumitra; Nie, Ben; Arnold, Robert D; Cummings, Brian S

    2016-05-01

    Lipids make up a diverse subset of biomolecules that are responsible for mediating a variety of structural and functional properties as well as modulating cellular functions such as trafficking, regulation of membrane proteins and subcellular compartmentalization. In particular, phospholipids are the main constituents of biological membranes and play major roles in cellular processes like transmembrane signaling and structural dynamics. The chemical and structural variety of lipids makes analysis using a single experimental approach quite challenging. Research in the field relies on the use of multiple techniques to detect and quantify components of cellular lipidomes as well as determine structural features and cellular organization. Understanding these features can allow researchers to elucidate the biochemical mechanisms by which lipid-lipid and/or lipid-protein interactions take place within the conditions of study. Herein, we provide an overview of essential methods for the examination of lipids, including extraction methods, chromatographic techniques and approaches for mass spectrometric analysis.

  11. Systematic investigation of ion suppression and enhancement effects of fourteen stable-isotope-labeled internal standards by their native analogues using atmospheric-pressure chemical ionization and electrospray ionization and the relevance for multi-analyte liquid chromatographic/mass spectrometric procedures.

    Science.gov (United States)

    Remane, Daniela; Wissenbach, Dirk K; Meyer, Markus R; Maurer, Hans H

    2010-04-15

    In clinical and forensic toxicology, multi-analyte procedures are very useful to quantify drugs and poisons of different classes in one run. For liquid chromatographic/tandem mass spectrometric (LC/MS/MS) multi-analyte procedures, often only a limited number of stable-isotope-labeled internal standards (SIL-ISs) are available. If an SIL-IS is used for quantification of other analytes, it must be excluded that the co-eluting native analyte influences its ionization. Therefore, the effect of ion suppression and enhancement of fourteen SIL-ISs caused by their native analogues has been studied. It could be shown that the native analyte concentration influenced the extent of ion suppression and enhancement effects leading to more suppression with increasing analyte concentration especially when electrospray ionization (ESI) was used. Using atmospheric-pressure chemical ionization (APCI), methanolic solution showed mainly enhancement effects, whereas no ion suppression and enhancement effect, with one exception, occurred when plasma extracts were used under these conditions. Such differences were not observed using ESI. With ESI, eleven SIL-ISs showed relevant suppression effects, but only one analyte showed suppression effects when APCI was used. The presented study showed that ion suppression and enhancement tests using matrix-based samples of different sources are essential for the selection of ISs, particularly if used for several analytes to avoid incorrect quantification. In conclusion, only SIL-ISs should be selected for which no suppression and enhancement effects can be observed. If not enough ISs are free of ionization interferences, a different ionization technique should be considered.

  12. Comparison of pigment content of paint samples using spectrometric methods

    Science.gov (United States)

    Trzcińska, Beata; Kowalski, Rafał; Zięba-Palus, Janina

    2014-09-01

    The aim of the paper was to evaluate the influence of pigment concentration and its distribution in polymer binder on the possibility of colour identification and paint sample comparison. Two sets of paint samples: one containing red and another one green pigment were prepared. Each set consisted of 13 samples differing gradually in the concentration of pigment. To obtain the sets of various colour shades white paint was mixed with the appropriate pigment in the form of a concentrated suspension. After solvents evaporation the samples were examined using spectrometric methods. The resin and main filler were identified by IR method. Colour and white pigments were identified on the base of Raman spectra. Colour of samples were compared based on Vis spectrometry according to colour theory. It was found that samples are homogenous (parameter measuring colour similarity ΔE < 3). The values of ΔE between the neighbouring samples in the set revealed decreasing linear function and between the first and following one - a logarithmic function.

  13. A Liquid Chromatographic-Mass Spectrometric (LC-MS) Method for the Analysis of the Bis-pyridinium Oxime ICD-585 in Plasma: Application in a Guinea Pig Model

    Science.gov (United States)

    2010-01-01

    pp. 78–80. 11] P. Taylor, in: J.H.Hardman, L.E. Limbird, P.B.Molinoff, R.W.Ruddon,A.Goodman Gilman (Eds.), Goodman &Gilman’s The Pharmacological Basis of Therapeutics, 9th ed., McGraw-Hill, New York, 1996, pp. 161–176.

  14. Gas chromatographic-mass spectrometric analysis of tar compounds formed during pyrolysis of rice husks

    NARCIS (Netherlands)

    Haanappel, V.A.C.; Stevens, T.W.; Hovestad, A.; Skolnik, V.; Visser, R.

    1991-01-01

    Pyrolysis of agricultural waste to produce fuel gas involves formation of tars as noxious by-products. In this paper the qualitative analysis of tars formed during pyrolysis of rice husks is presented, based on identification by gas chromatography—mass spectrometry and interpolation of retention tim

  15. Rapid headspace solid-phase microextraction-gas chromatographic-time-of-flight mass spectrometric method for qualitative profiling of ice wine volatile fraction. I. Method development and optimization.

    Science.gov (United States)

    Setkova, Lucie; Risticevic, Sanja; Pawliszyn, Janusz

    2007-04-20

    An analytical method for the determination of volatile and semi-volatile compounds representing various chemical groups in ice wines was developed and optimized in the presented study. A combination of the fully automated solid-phase microextraction (SPME) sample preparation technique and gas chromatographic-mass spectrometric (GC-MS) system to perform the final chromatographic separation and identification of the analytes of interest was utilized. A time-of-flight mass spectrometric (TOF-MS) analyzer provided very rapid analysis of this relatively complex matrix. Full spectral information in the range of m/z 35-450 was collected across the short GC run (less than 5 min). Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS) 50/30 microm fiber performed best during the optimization experiments and it was used in the headspace SPME mode to isolate compounds from ice wine samples, consisting of 3 mL wine with 1g salt addition. After the sample incubation and extraction (both 5 min at 45 degrees C), analytes were thermally desorbed in the GC injector for 2 min (injector maintained at 260 degrees C) and transferred into the column. The MS data acquisition rate of 50 spectra/s was selected as optimal. The optimized analytical method did not exceed 20 min per sample, including both the isolation and pre-concentration of the analytes of interest, the final GC-TOF-MS analysis and the fiber bake-out. Both a linear temperature-programmed retention index (LTPRI) method using C(8)-C(20) alkanes loaded onto the fiber and a mass spectral library search were employed to identify the target compounds. The repeatability of the developed and optimized HS-SPME-GC-TOF-MS method for ice wine analysis, expressed as relative standard deviation (RSD, %, n=7), ranged from 3.2 to 9.0%.

  16. Novel atomic absorption spectrometric and rapid spectrophotometric methods for the quantitation of paracetamol in saliva: Application to pharmacokinetic studies

    Directory of Open Access Journals (Sweden)

    Issa M

    2008-01-01

    Full Text Available A novel atomic absorption spectrometric method and two highly sensitive spectrophotometric methods were developed for the determination of paracetamol. These techniques based on the oxidation of paracetamol by iron (III (method I; oxidation of p-aminophenol after the hydrolysis of paracetamol (method II. Iron (II then reacts with potassium ferricyanide to form Prussian blue color with a maximum absorbance at 700 nm. The atomic absorption method was accomplished by extracting the excess iron (III in method II and aspirates the aqueous layer into air-acetylene flame to measure the absorbance of iron (II at 302.1 nm. The reactions have been spectrometrically evaluated to attain optimum experimental conditions. Linear responses were exhibited over the ranges 1.0-10, 0.2-2.0 and 0.1-1.0 µg/ml for method I, method II and atomic absorption spectrometric method, respectively. A high sensitivity is recorded for the proposed methods I and II and atomic absorption spectrometric method value indicate: 0.05, 0.022 and 0.012 µg/ml, respectively. The limit of quantitation of paracetamol by method II and atomic absorption spectrometric method were 0.20 and 0.10 µg/ml. Method II and the atomic absorption spectrometric method were applied to demonstrate a pharmacokinetic study by means of salivary samples in normal volunteers who received 1.0 g paracetamol. Intra and inter-day precision did not exceed 6.9%.

  17. Standard test methods for chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade boron carbide

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2004-01-01

    1.1 These test methods cover procedures for the chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade boron carbide powder and pellets to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Total Carbon by Combustion and Gravimetry 7-17 Total Boron by Titrimetry 18-28 Isotopic Composition by Mass Spectrometry 29-38 Chloride and Fluoride Separation by Pyrohydrolysis 39-45 Chloride by Constant-Current Coulometry 46-54 Fluoride by Ion-Selective Electrode 55-63 Water by Constant-Voltage Coulometry 64-72 Impurities by Spectrochemical Analysis 73-81 Soluble Boron by Titrimetry 82-95 Soluble Carbon by a Manometric Measurement 96-105 Metallic Impurities by a Direct Reader Spectrometric Method 106-114

  18. Heterogeneous nuclear ribonucleoproteins C1/C2 identified as autoantigens by biochemical and mass spectrometric methods

    DEFF Research Database (Denmark)

    Heegaard, N H; Larsen, Martin Røssel; Muncrief, T

    2000-01-01

    The antigenic specificity of an unusual antinuclear antibody pattern in three patient sera was identified after separating HeLa-cell nuclear extracts by two-dimensional (2D) gel electrophoresis and localizing the antigens by immunoblotting with patient serum. Protein spots were excised from the 2......-separation methods and mass-spectrometric peptide mapping in combination with database searches are powerful tools in the identification of novel autoantigen specificities....

  19. Standard test methods for chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade plutonium metal

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2004-01-01

    1.1 These test methods cover procedures for the chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade plutonium metal to determine compliance with specifications.

  20. Recent developments of nanoparticle-based enrichment methods for mass spectrometric analysis in proteomics

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    In proteome research, rapid and effective separation strategies are essential for successful protein identification due to the broad dynamic range of proteins in biological samples. Some important proteins are often expressed in ultra low abundance, thus making the pre-concentration procedure before mass spectrometric analysis prerequisite. The main purpose of enrichment is to isolate target molecules from complex mixtures to reduce sample complexity and facilitate the subsequent analyzing steps. The introduction of nanoparticles into this field has accelerated the development of enrichment methods. In this review, we mainly focus on recent developments of using different nanomaterials for pre-concentration of low-abundance peptides/ proteins, including those containing post-translational modifications, such as phosphorylation and glycosylation, prior to mass spectrometric analysis.

  1. Neutron spectrometric methods for core inventory verification in research reactors

    CERN Document Server

    Ellinger, A; Hansen, W; Knorr, J; Schneider, R

    2002-01-01

    In consequence of the Non-Proliferation Treaty safeguards, inspections are periodically made in nuclear facilities by the IAEA and the EURATOM Safeguards Directorate. The inspection methods are permanently improved. Therefore, the Core Inventory Verification method is being developed as an indirect method for the verification of the core inventory and to check the declared operation of research reactors.

  2. Improved method for the analysis of organic acids and new derivatization of alcohols in complex natural aqueous matrixes: application to wine and apple vinegar.

    Science.gov (United States)

    Giumanini, A G; Verardo, G; Della Martina, D; Toniutti, N

    2001-06-01

    An improvement in the procedure for investigation of organic acids and a new derivatization method, amenable to gas chromatographic-mass spectrometric detection of alcohols, are presented. The latter is based on the formation of phenacetyl esters. The simultaneous application of the two methods also allows data to be obtained on some volatile neutrals present in complex natural aqueous fluids. Application to wine and cider vinegars allowed detection of a number of previously unreported components, among which are interesting partially esterified polycarboxylic esters.

  3. Extending the frontiers of mass spectrometric instrumentation and methods

    Energy Technology Data Exchange (ETDEWEB)

    Schieffer, Gregg Martin [Iowa State Univ., Ames, IA (United States)

    2010-01-01

    The focus of this dissertation is two-fold: developing novel analysis methods using mass spectrometry and the implementation and characterization of a novel ion mobility mass spectrometry instrumentation. The novel mass spectrometry combines ion trap for ion/ion reactions coupled to an ion mobility cell. The long term goal of this instrumentation is to use ion/ion reactions to probe the structure of gas phase biomolecule ions. The three ion source - ion trap - ion mobility - qTOF mass spectrometer (IT - IM - TOF MS) instrument is described. The analysis of the degradation products in coal (Chapter 2) and the imaging plant metabolites (Appendix III) fall under the methods development category. These projects use existing commercial instrumentation (JEOL AccuTOF MS and Thermo Finnigan LCQ IT, respectively) for the mass analysis of the degraded coal products and the plant metabolites, respectively. The coal degradation paper discusses the use of the DART ion source for fast and easy sample analysis. The sample preparation consisted of a simple 50 fold dilution of the soluble coal products in water and placing the liquid in front of the heated gas stream. This is the first time the DART ion source has been used for analysis of coal. Steven Raders under the guidance of John Verkade came up with the coal degradation projects. Raders performed the coal degradation reactions, worked up the products, and sent them to me. Gregg Schieffer developed the method and wrote the paper demonstrating the use of the DART ion source for the fast and easy sample analysis. The plant metabolite imaging project extends the use of colloidal graphite as a sample coating for atmospheric pressure LDI. DC Perdian and I closely worked together to make this project work. Perdian focused on building the LDI setup whereas Schieffer focused on the MSn analysis of the metabolites. Both Perdian and I took the data featured in the paper. Perdian was the primary writer of the paper and used it as a

  4. Spectrometric methods used in the calibration of radiodiagnostic measuring instruments

    Energy Technology Data Exchange (ETDEWEB)

    De Vries, W. [Rijksuniversiteit Utrecht (Netherlands)

    1995-12-01

    Recently a set of parameters for checking the quality of radiation for use in diagnostic radiology was established at the calibration facility of Nederlands Meetinstituut (NMI). The establishment of the radiation quality required re-evaluation of the correction factors for the primary air-kerma standards. Free-air ionisation chambers require several correction factors to measure air-kerma according to its definition. These correction factors were calculated for the NMi free-air chamber by Monte Carlo simulations for monoenergetic photons in the energy range from 10 keV to 320 keV. The actual correction factors follow from weighting these mono-energetic correction factors with the air-kerma spectrum of the photon beam. This paper describes the determination of the photon spectra of the X-ray qualities used for the calibration of dosimetric instruments used in radiodiagnostics. The detector used for these measurements is a planar HPGe-detector, placed in the direct beam of the X-ray machine. To convert the measured pulse height spectrum to the actual photon spectrum corrections must be made for fluorescent photon escape, single and multiple compton scattering inside the detector, and detector efficiency. From the calculated photon spectra a number of parameters of the X-ray beam can be calculated. The calculated first and second half value layer in aluminum and copper are compared with the measured values of these parameters to validate the method of spectrum reconstruction. Moreover the spectrum measurements offer the possibility to calibrate the X-ray generator in terms of maximum high voltage. The maximum photon energy in the spectrum is used as a standard for calibration of kVp-meters.

  5. Mass spectrometric methods for the direct elemental and isotopic analysis of solid material

    Science.gov (United States)

    Ganeev, A. A.; Gubal, A. R.; Potapov, S. V.; Agafonova, N. N.; Nemets, V. M.

    2016-04-01

    Methods for the direct analysis of solids have a number of undeniable advantages over the methods that require preliminary dissolution of samples. High sensitivity and selectivity make the direct mass spectrometric techniques the most in-demand. The review concerns spark source mass spectrometry, laser ionization mass spectrometry, laser ablation inductively coupled plasma mass spectrometry, secondary ion mass spectrometry, secondary neutral mass spectrometry and glow discharge mass spectrometry. Basic principles, analytical characteristics and trends in the development of these techniques are discussed. Particular attention is given to applications of the techniques as well as to their competitive advantages and drawbacks. The bibliography includes 123 references.

  6. Mass spectrometric immunoassay

    Science.gov (United States)

    Nelson, Randall W; Williams, Peter; Krone, Jennifer Reeve

    2007-12-04

    Rapid mass spectrometric immunoassay methods for detecting and/or quantifying antibody and antigen analytes utilizing affinity capture to isolate the analytes and internal reference species (for quantification) followed by mass spectrometric analysis of the isolated analyte/internal reference species. Quantification is obtained by normalizing and calibrating obtained mass spectrum against the mass spectrum obtained for an antibody/antigen of known concentration.

  7. Standard test methods for chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of uranium hexafluoride

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2011-01-01

    1.1 These test methods cover procedures for subsampling and for chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of uranium hexafluoride UF6. Most of these test methods are in routine use to determine conformance to UF6 specifications in the Enrichment and Conversion Facilities. 1.2 The analytical procedures in this document appear in the following order: Note 1—Subcommittee C26.05 will confer with C26.02 concerning the renumbered section in Test Methods C761 to determine how concerns with renumbering these sections, as analytical methods are replaced with stand-alone analytical methods, are best addressed in subsequent publications. Sections Subsampling of Uranium Hexafluoride 7 - 10 Gravimetric Determination of Uranium 11 - 19 Titrimetric Determination of Uranium 20 Preparation of High-Purity U3O 8 21 Isotopic Analysis 22 Isotopic Analysis by Double-Standard Mass-Spectrometer Method 23 - 29 Determination of Hydrocarbons, Chlorocarbons, and Partially Substitut...

  8. Gas chromatography-mass spectrometric method for metabolic profiling of tobacco leaves.

    Science.gov (United States)

    Li, Yong; Pang, Tao; Li, Yanli; Wang, Xiaolin; Li, Qinghua; Lu, Xin; Xu, Guowang

    2011-06-01

    A gas chromatography-mass spectrometric method was developed for profiling of tobacco leaves. The differentiation among tobacco leaves planted in two different regions was investigated. Prior to analysis, the extraction solvent formulation was optimized and a combination of water, methanol and acetonitrile with a volume ratio of 3:1:1 was found to be optimal. The reproducibility of the method was satisfactory. Kendall tau-b rank correlation coefficients were equal to 1 (pleaves from Zimbabwe and Yunnan of China. Our result revealed that levels of saccharides and their derivatives including xylose, ribose, fructose, glucose, turanose, xylitol and glyceric acid were more abundant while sucrose, glucitol and D-gluconic acid were less abundant in tobacco leaves from Yunnan as compared to those from Zimbabwe. Amino acids such as L-alanine, L-tyrosine and L-threonine were found to be richer in Zimbabwe tobacco than in Yunnan tobacco.

  9. Determination of cyanide by a flow injection analysis-atomic absorption spectrometric method.

    Science.gov (United States)

    López Gómez, A V; Martínez Calatayud, J

    1998-10-01

    A new flow injection analysis (FIA) procedure is proposed for the indirect atomic absorption spectrometric determination of cyanide. The FIA manifold is based on the insertion of the sample into a distilled water carrier, then the sample flows through a solid-phase reactor filled with silver iodide entrapped in polymeric resin beads. The calibration graph is linear over the range 0.2-6.0 mg l-1 of cyanide (correlation coefficient 0.9974), the detection limit is 0.1 mg l-1, the sample throughput is 193 h-1 and the RSD is 0.8%. The method is simple, quick and more selective than other published FIA procedures. The reproducibility obtained by using different solid-phase reactors and solutions is in the range 2.2-3.1% (RSD). The method was applied to the determination of cyanide in commercial samples such as pharmaceutical formulations and industrial electrolytic baths.

  10. Method and apparatus for enhanced sequencing of complex molecules using surface-induced dissociation in conjunction with mass spectrometric analysis

    Science.gov (United States)

    Laskin, Julia [Richland, WA; Futrell, Jean H [Richland, WA

    2008-04-29

    The invention relates to a method and apparatus for enhanced sequencing of complex molecules using surface-induced dissociation (SID) in conjunction with mass spectrometric analysis. Results demonstrate formation of a wide distribution of structure-specific fragments having wide sequence coverage useful for sequencing and identifying the complex molecules.

  11. Gas chromatographic-mass spectrometric analysis of essential oils from Pimpinella species gathered from Central and Northern Turkey.

    Science.gov (United States)

    Tabanca, Nurhayat; Demirci, Betul; Ozek, Temel; Kirimer, Nese; Baser, K Husnu Can; Bedir, Erdal; Khan, Ikhlas A; Wedge, David E

    2006-06-09

    Essential oils from 15 Pimpinella species were analyzed by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) techniques. One species, Pimpinella anisum, in which only fruits were evaluated, was also included in the study. A total of 140 different compounds were identified and significant qualitative and quantitative differences were observed among the samples. Pimpinella essential oils were characterized as having mono-, sesqui- and trinorsesquiterpenoids, propenylphenols, and pseudoisoeugenols. Trinorsesquiterpenoids and phenylpropanoids appear to be chemical markers of Pimpinella species analyzed thus far. Essential oils obtained from Pimpinella roots share the same principal compound, epoxypseudoisoeugenyl-2-methylbutyrate at concentrations from 20 to 82.6%.

  12. Gas purge microsyringe extraction for quantitative direct gas chromatographic-mass spectrometric analysis of volatile and semivolatile chemicals.

    Science.gov (United States)

    Yang, Cui; Piao, Xiangfan; Qiu, Jinxue; Wang, Xiaoping; Ren, Chunyan; Li, Donghao

    2011-03-25

    Sample pretreatment before chromatographic analysis is the most time consuming and error prone part of analytical procedures, yet it is a key factor in the final success of the analysis. A quantitative and fast liquid phase microextraction technique termed as gas purge microsyringe extraction (GP-MSE) has been developed for simultaneous direct gas chromatography-mass spectrometry (GC-MS) analysis of volatile and semivolatile chemicals without cleanup process. Use of a gas flowing system, temperature control and a conventional microsyringe greatly increased the surface area of the liquid phase micro solvent, and led to quantitative recoveries of both volatile and semivolatile chemicals within short extraction time of only 2 min. Recoveries of polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and alkylphenols (APs) determined were 85-107%, and reproducibility was between 2.8% and 8.5%. In particular, the technique shows high sensitivity for semivolatile chemicals which is difficult to achieve in other sample pretreatment techniques such as headspace-liquid phase microextraction. The variables affecting extraction efficiency such as gas flow rate, extraction time, extracting solvent type, temperature of sample and extracting solvent were investigated. Finally, the technique was evaluated to determine PAHs, APs and OCPs from plant and soil samples. The experimental results demonstrated that the technique is economic, sensitive to both volatile and semivolatile chemicals, is fast, simple to operate, and allows quantitative extraction. On-site monitoring of volatile and semivolatile chemicals is now possible using this technique due to the simplification and speed of sample treatment.

  13. Antioxidant activity and gas chromatographic-mass spectrometric analysis of extracts of the marine algae, caulerpa peltata and padina gymnospora

    Directory of Open Access Journals (Sweden)

    Kavitha Murugan

    2014-01-01

    Full Text Available The results of our previous investigations on extracts of selected marine algae showed that Caulerpa peltata and Padina gymnospora had more promising antiproliferative and antioxidant activities than Gelidiella acerosa and Sargassum wightii. Based on these results, the more active chloroform extract of C. peltata and ethyl acetate extract of P. gymnospora were further analyzed for their constituents by using gas chromatography in tandem with mass spectrometry. The GC-MS analysis (GC % peak area given in parentheses showed that fucosterol (12.45% and L-(+-ascorbic acid 2,6-dihexadecanoate (8.13% were the major compounds present in P. gymnospora ethyl acetate extract. On the other hand, C. peltata chloroform extract had 1-heptacosanol (10.52%, hexacosanol acetate (9.28%, tetradecyl ester of chloroacetic acid (7.22%, Z,Z-6,28-heptatriactontadien-2-one (6.77% and 10,13-dimethyl-methyl ester of tetradecanoic acid (5.34% as major compounds. Also described in the report are the beta-carotene bleaching inhibitory and total reducing activities of the chloroform and ethyl acetate extracts of C. peltata and P. gymnospora, respectively, relative to the other three extracts (aqueous, methanol, chloroform or ethyl acetate of the two algae.

  14. Gas chromatographic-mass spectrometric characterisation of amiton and the recovery of amiton from concrete, paint, rubber and soil matrices.

    Science.gov (United States)

    Borrett, Veronica T; Gan, Tiang-Hong; Lakeland, Barry R; Leslie, D Ralph; Mathews, Robert J; Mattsson, Eric R; Riddell, Stuart; Tantaro, Vince

    2003-06-27

    Amiton [O,O-diethyl S-[2-(diethylamino)ethyl] phosphorothiolate], is an organophosphorus chemical included in Schedule 2 of the Chemical Weapons Convention (CWC). Verification provisions under the CWC rely on the existence of a database of analytical information for scheduled chemicals and related compounds. Little analytical information is available for amiton. In this study, gas chromatography-mass spectrometry (GC-MS) characterisation of amiton and its typical impurities (including by-products and degradation products), supported by selective GC detection and 31P NMR data, was undertaken. Twenty-one compounds, including a by-product unique to amiton from an industrial source, were identified. Involatile degradation products of amiton were derivatised to enable their identification by GC-MS. The recovery of amiton from matrices that may be expected in an inspection scenario (i.e. concrete, paint, rubber and soil) was also examined. Paint and concrete matrices were the most useful matrices for the detection of amiton, and its by-products and degradation products. Amiton was readily detected in these matrices after 28 days.

  15. Liquid chromatographic-mass spectrometric analysis of anthocyanin composition of dark blue bee pollen from Echium plantagineum.

    Science.gov (United States)

    Di Paola-Naranjo, Romina Daniela; Sánchez-Sánchez, José; González-Paramás, Ana María; Rivas-Gonzalo, Julián Carlos

    2004-10-29

    Dark blue bee pollen samples from pollinic type Echium plantegineum were analysed in order to identify and quantify their anthocyanin pigments. Five samples were collected from different apicultural Spanish regions and the anthocyanin composition was determined by HPLC with diode array and MS detection. Eight different pigments were identified, the principal anthocyanin being petunidin-3-O-rutinoside. The other pigments found were delphinidin, cyanidin and petunidin-3-O-glucoside; delphinidin, cyanidin, peonidin and malvidin-3-O-rutinoside and cyanidin-3-(6"-malonylglucoside). The anthocyanin content ranged from 45 to 80 mg/100 g of blue pollen, which could represent a significant source of phytochemicals. Minor variations in the anthocyanin profiles were found, which could be explained by the geographical differences between collection regions.

  16. Sublimation as a method of matrix application for mass spectrometric imaging.

    Science.gov (United States)

    Hankin, Joseph A; Barkley, Robert M; Murphy, Robert C

    2007-09-01

    Common organic matrix-assisted laser desorption/ionization (MALDI) matrices, 2,5-dihydroxybenzoic acid, 3,5-dimethoxy-4-hydroxycinnamic acid, and alpha-cyano-4-hydroxycinnamic acid, were found to undergo sublimation without decomposition under conditions of reduced pressure and elevated temperature. This solid to vapor-phase transition was exploited to apply MALDI matrix onto tissue samples over a broad surface in a solvent-free application for mass spectrometric imaging. Sublimation of matrix produced an even layer of small crystals across the sample plate. The deposition was readily controlled with time, temperature, and pressure settings and was highly reproducible from one sample to the next. Mass spectrometric images acquired from phospholipid standards robotically spotted onto a MALDI plate yielded a more intense, even signal with fewer sodium adducts when matrix was applied by sublimation relative to samples where matrix was deposited by an electrospray technique. MALDI matrix could be readily applied to tissue sections on glass slides and stainless steel MALDI plate inserts as long as good thermal contact was made with the condenser of the sublimation device. Sections of mouse brain were coated with matrix applied by sublimation and were imaged using a Q-q-TOF mass spectrometer to yield mass spectral images of very high quality. Image quality is likely enhanced by several features of this technique including the microcrystalline morphology of the deposited matrix, increased purity of deposited matrix, and evenness of deposition. This inexpensive method was reproducible and eliminated the potential for spreading of analytes arising from solvent deposition during matrix application.

  17. Spectrometric techniques 4

    CERN Document Server

    Vanasse, George A

    2013-01-01

    Spectrometric Techniques, Volume IV discusses three widely diversified areas of spectrometric techniques. The book focuses on three spectrometric methods. Chapter 1 discusses the phenomenology and applications of Coherent Anti-Stokes Raman Spectroscopy (CARS), the most commonly used optical technique that exploit the Raman effect. The second chapter is concerned with diffraction gratings and mountings for the Vacuum Ultraviolet Spectral Region. Chapter 3 accounts the uses of mass spectrometry, detectors, types of spectrometers, and ion sources. Physicists and chemists will find the book a go

  18. Standard test methods for chemical and mass spectrometric analysis of nuclear-grade gadolinium oxide (Gd2O3) powder

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2006-01-01

    1.1 These test methods cover procedures for the chemical and mass spectrometric analysis of nuclear-grade gadolinium oxide powders to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Carbon by Direct CombustionThermal Conductivity C1408 Test Method for Carbon (Total) in Uranium Oxide Powders and Pellets By Direct Combustion-Infrared Detection Method Total Chlorine and Fluorine by Pyrohydrolysis Ion Selective Electrode C1502 Test Method for Determination of Total Chlorine and Fluorine in Uranium Dioxide and Gadolinium Oxide Loss of Weight on Ignition 7-13 Sulfur by CombustionIodometric Titration Impurity Elements by a Spark-Source Mass Spectrographic C761 Test Methods for Chemical, Mass Spectrometric, Spectrochemical,Nuclear, and Radiochemical Analysis of Uranium Hexafluoride C1287 Test Method for Determination of Impurities In Uranium Dioxide By Inductively Coupled Plasma Mass Spectrometry Gadolinium Content in Gadolinium Oxid...

  19. Stable isotope dilution analysis of salicylic acid and hydroquinone in human skin samples by gas chromatography with mass spectrometric detection.

    Science.gov (United States)

    Judefeind, Anja; van Rensburg, Peet Jansen; Langelaar, Stephan; du Plessis, Jeanetta

    2007-06-01

    A sensitive and accurate gas chromatographic-mass spectrometric (GC-MS) method has been developed for the quantitative determination of salicylic acid (SA) and hydroquinone (HQ) from human skin samples and cosmetic emulsions. Deuterium labeled SA-d(6) and HQ-d(6) were used as internal standards (IS). The samples were extracted with methanol, dried under nitrogen and derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA)+1% trimethylchlorosilane (TMCS). Quantification was performed in SIM mode with a limit of quantification (LOQ) of 50 ng ml(-1) for SA and 10 ng ml(-1) for HQ. The inter-day variation (R.S.D.) was less than 5% and the accuracy was better than 13.3% for both compounds. The recoveries from the different matrices ranged between 93.1 and 103.3% for SA, and 97.3 and 100.8% for HQ.

  20. A hybrid sorption - Spectrometric method for determination of synthetic anionic dyes in foodstuffs.

    Science.gov (United States)

    Tikhomirova, Tatyana I; Ramazanova, Gyulselem R; Apyari, Vladimir V

    2017-04-15

    A sorption-spectrometric method for determination of the anionic synthetic dyes based on their sorption on silica sorbent modified with hexadecyl groups (C16) followed by measuring the diffuse reflectance spectra on the surface of the sorbent has been proposed. Adsorption of sulfonated azo dyes Tartrazine (E102), Sunset Yellow FCF (E110), Ponceau 4R (E124) reaches maximum in acidic medium (1M HCl - pH 1). For the quinophthalone type dye Quinoline Yellow (E104), the adsorption is also maximal in an acidic medium (1M HCl - pH 2). The triphenylmethane dye Fast Green FCF (E143) is absorbed in the wider area of pH (1M HCl - pH 6). Increasing concentration of the dyes in a solution led to the increase in absorption band intensity in diffuse reflectance spectra of the adsorbent, which was used for their direct determination. The proposed method was applied to the determination of dyes in beverages and pharmaceuticals.

  1. Detection of geosmin and 2-methylisoborneol by liquid-liquid extraction-gas chromatograph mass spectrum (LLE-GCMS)and solid phase extraction-gas chromatograph mass spectrum (SPE-GCMS)

    Institute of Scientific and Technical Information of China (English)

    MA Xiaoyan; GAO Naiyun; CHEN Beibei; LI Qingsong; ZHANG Qiaoli; GU Guofen

    2007-01-01

    Two sample preparation methods were introduced and compared in this paper to establish a simple,quick and exact analysis of geosmin and 2-methylisoborneol.LC-18 column was employed in solid phase extraction (SPE),1.0 mL of hexane was adopted in liquid-liquid extraction(LLE),and the extracts were analyzed by gas chromatograph mass spectrum (GCMS) in selected ion mode.Mean recoveries of SPE were low for 2-methylisoborneol (2-MIB)and geosmin (GSM) with values below 50%.For LLE,the recoveries were satisfyingly above 50% for 2-MIB and 80% for GSM.Detection limits of the LLE method were as low as 1.0 ng/L for GSM and 5.0 ng/L for 2-MIB.A year-long investigation on odor chemicals of drinking water in Shanghai demonstrated that in the summer,there was a serious odor problem induced by a high concentration of 2-MIB.The highest concentration of 152.82 ng/L appeared in July in raw water,while GSM flocculation was minimal with concentrations below odor threshold.

  2. Mass Spectrometric Method for Analyzing Metabolites in Yeast with Single Cell Sensitivity

    NARCIS (Netherlands)

    Amantonico, Andrea; Oh, Joo Yeon; Sobek, Jens; Heinemann, Matthias; Zenobi, Renato

    2008-01-01

    Getting a look-in: An optimized MALDI-MS procedure has been developed to detect endogenous primary metabolites directly in the cell extract. A detection limit corresponding to metabolites from less than a single cell has been attained, opening the door to single-cell metabolomics by mass spectrometr

  3. Standard test methods for chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade plutonium nitrate solutions

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2010-01-01

    1.1 These test methods cover procedures for the chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade plutonium nitrate solutions to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Plutonium by Controlled-Potential Coulometry Plutonium by Amperometric Titration with Iron(II) Plutonium by Diode Array Spectrophotometry Free Acid by Titration in an Oxalate Solution 8 to 15 Free Acid by Iodate Precipitation-Potentiometric Titration Test Method 16 to 22 Uranium by Arsenazo I Spectrophotometric Test Method 23 to 33 Thorium by Thorin Spectrophotometric Test Method 34 to 42 Iron by 1,10-Phenanthroline Spectrophotometric Test Method 43 to 50 Impurities by ICP-AES Chloride by Thiocyanate Spectrophotometric Test Method 51 to 58 Fluoride by Distillation-Spectrophotometric Test Method 59 to 66 Sulfate by Barium Sulfate Turbidimetric Test Method 67 to 74 Isotopic Composition by Mass Spectrom...

  4. Determination of Sulfur Compound in Liquefied Petroleum Gas and Liquefied Natural Gas by Gas Chromatographic-mass Spectrometric Method%用气相色谱-质谱法分析液化石油气和液化天然气中的硫化合物含量

    Institute of Scientific and Technical Information of China (English)

    周宏标

    2002-01-01

    研究了用气相色谱-质谱联用测定天然气中硫化合物,分析了从不同油田收集的天然气样品,所得结果精密度及准确度良好,每种硫化合物的检测极限都在1×10-6之下(质量比).

  5. Advanced hyphenated chromatographic-mass spectrometry in mycotoxin determination: current status and prospects.

    Science.gov (United States)

    Li, Peiwu; Zhang, Zhaowei; Hu, Xiaofeng; Zhang, Qi

    2013-01-01

    Mass spectrometric techniques are essential for advanced research in food safety and environmental monitoring. These fields are important for securing the health of humans and animals, and for ensuring environmental security. Mycotoxins, toxic secondary metabolites of filamentous fungi, are major contaminants of agricultural products, food and feed, biological samples, and the environment as a whole. Mycotoxins can cause cancers, nephritic and hepatic diseases, various hemorrhagic syndromes, and immune and neurological disorders. Mycotoxin-contaminated food and feed can provoke trade conflicts, resulting in massive economic losses. Risk assessment of mycotoxin contamination for humans and animals generally depends on clear identification and reliable quantitation in diversified matrices. Pioneering work on mycotoxin quantitation using mass spectrometry (MS) was performed in the early 1970s. Now, unambiguous confirmation and quantitation of mycotoxins can be readily achieved with a variety hyphenated techniques that combine chromatographic separation with MS, including liquid chromatography (LC) or gas chromatography (GC). With the advent of atmospheric pressure ionization, LC-MS has become a routine technique. Recently, the co-occurrence of multiple mycotoxins in the same sample has drawn an increasing amount of attention. Thus, modern analyses must be able to detect and quantitate multiple mycotoxins in a single run. Improvements in tandem MS techniques have been made to achieve this purpose. This review describes the advanced research that has been done regarding mycotoxin determination using hyphenated chromatographic-MS techniques, but is not a full-circle survey of all the literature published on this topic. The present work provides an overview of the various hyphenated chromatographic-MS-based strategies that have been applied to mycotoxin analysis, with a focus on recent developments. The use of chromatographic-MS to measure levels of mycotoxins, including

  6. Critical comparison of radiometric and mass spectrometric methods for the determination of radionuclides in environmental, biological and nuclear waste samples.

    Science.gov (United States)

    Hou, Xiaolin; Roos, Per

    2008-02-11

    The radiometric methods, alpha (alpha)-, beta (beta)-, gamma (gamma)-spectrometry, and mass spectrometric methods, inductively coupled plasma mass spectrometry, accelerator mass spectrometry, thermal ionization mass spectrometry, resonance ionization mass spectrometry, secondary ion mass spectrometry, and glow discharge mass spectrometry are reviewed for the determination of radionuclides. These methods are critically compared for the determination of long-lived radionuclides important for radiation protection, decommissioning of nuclear facilities, repository of nuclear waste, tracer application in the environmental and biological researches, these radionuclides include (3)H, (14)C, (36)Cl, (41)Ca, (59,63)Ni, (89,90)Sr, (99)Tc, (129)I, (135,137)Cs, (210)Pb, (226,228)Ra, (237)Np, (241)Am, and isotopes of thorium, uranium and plutonium. The application of on-line methods (flow injection/sequential injection) for separation of radionuclides and automated determination of radionuclides is also discussed.

  7. Development of an Isotope-Dilution Liquid Chromatography/Mass Spectrometric Method for the Accurate Determination of Acetaminophen in Tablets

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Hyun Ju; Kim, Byung Joo; Lee, Joon Hee; Hwang, Eui Jin [Korea Research Institute of Standards and Science, Daejeon (Korea, Republic of)

    2010-12-15

    Acetaminophen (N-acetyl-p-aminophenol) is one of the most popular analgesic and antipyretic drugs. An isotope dilution mass spectrometric method based on LC/MS was developed as a candidate reference method for the accurate determination of acetaminophen in pharmaceutical product. After spiking an isotope labeled acetaminophen (acetyl-{sup 13}C{sub 2}, {sup 15}Nacetaminophen) as an internal standard, tablet extracts were analyzed by LC/MS in a selected reaction monitoring (SRM) mode to detect ions at m/z 152→110 and m/z 155→111 for acetaminophen and acetyl-{sup 13}C{sub 2}, {sup 15}N-acetaminophen, respectively. The repeatability and reproducibility of the developed ID/LC-MS method were tested for the validation and assessment of metrological quality of the method.

  8. Standard test methods for chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solutions

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    1999-01-01

    1.1 These test methods cover procedures for the chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solution to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Determination of Uranium 7 Specific Gravity by Pycnometry 15-20 Free Acid by Oxalate Complexation 21-27 Determination of Thorium 28 Determination of Chromium 29 Determination of Molybdenum 30 Halogens Separation by Steam Distillation 31-35 Fluoride by Specific Ion Electrode 36-42 Halogen Distillate Analysis: Chloride, Bromide, and Iodide by Amperometric Microtitrimetry 43 Determination of Chloride and Bromide 44 Determination of Sulfur by X-Ray Fluorescence 45 Sulfate Sulfur by (Photometric) Turbidimetry 46 Phosphorus by the Molybdenum Blue (Photometric) Method 54-61 Silicon by the Molybdenum Blue (Photometric) Method 62-69 Carbon by Persulfate Oxidation-Acid Titrimetry 70 Conversion to U3O8 71-74 Boron by ...

  9. Standard test methods for chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade plutonium dioxide powders and pellets

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2010-01-01

    1.1 These test methods cover procedures for the chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade plutonium dioxide powders and pellets to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Plutonium Sample Handling 8 to 10 Plutonium by Controlled-Potential Coulometry Plutonium by Ceric Sulfate Titration Plutonium by Amperometric Titration with Iron(II) Plutonium by Diode Array Spectrophotometry Nitrogen by Distillation Spectrophotometry Using Nessler Reagent 11 to 18 Carbon (Total) by Direct Combustion–Thermal Conductivity 19 to 30 Total Chlorine and Fluorine by Pyrohydrolysis 31 to 38 Sulfur by Distillation Spectrophotometry 39 to 47 Plutonium Isotopic Analysis by Mass Spectrometry Rare Earth Elements by Spectroscopy 48 to 55 Trace Elements by Carrier–Distillation Spectroscopy 56 to 63 Impurities by ICP-AES Impurity Elements by Spark-Source Mass Spectrography 64 to 70 Moisture by the Coulomet...

  10. Differentiation of the four major types (C. Burmannii, C. Verum, C. cassia, And C. Loureiroi) of cinnamons using a flow-injection mass spectrometric (FIMS) fingerprinting method

    Science.gov (United States)

    A simple and efficient flow-injection mass spectrometric (FIMS) method was developed to differentiate cinnamon (Cinnamomum) bark (CB) samples of the four major species (C. burmannii, C. verum, C. aromaticum, and C. loureiroi) of cinnamon. Fifty cinnamon samples collected from China, Vietnam, Indon...

  11. Development of gamma spectrometric method for the determination of thorium in phosphoric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Mirashi, N.N.; Chaudhury, S.; Aggarwal, S.K. [Fuel Chemistry Div., Bhabha Atomic Research Centre, Mumbai (India)

    2010-07-01

    Gamma spectrometric determination of thorium in sintered thoria dissolved in strong phosphoric acid was studied using a high purity germanium (HPGe) detector. {sup 232}Th was determined using the highly abundant (27%) gamma ray (911.4 keV) emitted by its daughter {sup 228}Ac. The count rates in peak regions were plotted against the amount of thorium present in thorium nitrate working standard solution to obtain a calibration curve and the extent of thoria dissolved in 88% phosphoric acid was determined. Further studies on determination of thorium were carried out using thorium phosphate solutions, instead of using thorium nitrate working standard solutions. The solution of thorium phosphate obtained after quantitative dissolution of thoria in 88% phosphoric acid was also found to give a linear calibration curve at 911.4 keV. Using the calibration curves, expected count rates for thorium in sintered thoria dissolved in 88% phosphoric acid were calculated and were in good agreement ({+-}3%) with the observed count rates. (orig.)

  12. Development and validation of a liquid chromatographic-electrospray tandem mass spectrometric multiresidue method for anthelmintics in milk.

    Science.gov (United States)

    De Ruyck, Hendrik; Daeseleire, Els; De Ridder, Herman; Van Renterghem, Roland

    2002-11-08

    A liquid chromatographic-tandem mass spectrometric multiresidue method for the simultaneous quantitative determination of the tetrahydroimidazole, levamisole and the benzimidazoles thiabendazole, oxfendazole, oxibendazole, albendazole, fenbendazole, febantel and triclabendazole in milk has been developed and validated. The anthelmintic residues were extracted with ethyl acetate. The liquid chromatographic separation was performed on a reversed-phase C18 column with gradient elution. The analytes were detected by tandem quadrupole mass spectrometry after positive electrospray ionisation by multiple reaction monitoring. The confirmatory method is very sensitive and each component can be detected at a residue level lower than 1 microgram/l. The method is validated according to the revised European Union requirements and all parameters were found conform the criteria. The evaluated parameters were linearity, specificity, stability, recovery, precision (repeatability and within-laboratory reproducibility) and analytical limits (detection limit, decision limit and detection capability). This analytical method is applied in the Belgian monitoring programme for classical anthelmintic veterinary drugs in raw farm cow's milk.

  13. Development and validation of a liquid chromatographic-tandem mass spectrometric method for determination of eleven coccidiostats in milk.

    Science.gov (United States)

    Nász, Szilárd; Debreczeni, Lajos; Rikker, Tamás; Eke, Zsuzsanna

    2012-07-15

    A reversed phase liquid chromatographic-tandem mass spectrometric method with simple solvent extraction and purification by solid phase extraction (SPE) has been developed for the determination of coccidiostats in milk. For sample preparation matrix solid phase dispersion, extraction by organic solvent and SPE with different cartridges were also tested. The compounds determined include lasalocid, narasin, salinomycin, monensin, semduramicin, maduramicin, robenidine, decoquinate, halofuginone, nicarbazin and diclazuril. Main steps of the method are addition of acetonitrile to the milk samples, centrifugation, removal of matrix by SPE, concentration by evaporation and LC-MS-MS determination. During a 15 min time segmented chromatographic run compounds are ionised either positively or negatively. Calculated recoveries range between 77.1% and 118.2%. Maximum levels are in the range of 1-20 μg/kg. The developed method was validated in line with the requirements of Commission Decision 2002/657/EC (2002). It is applicable for control of coccidiostat residues in milk as indicated in Regulation 124/2009/EC (2009).

  14. iTRAQ-based profiling of grape berry exocarp proteins during ripening using a parallel mass spectrometric method.

    Science.gov (United States)

    Martínez-Esteso, Maria José; Casado-Vela, Juan; Sellés-Marchart, Susana; Elortza, Felix; Pedreño, Maria Angeles; Bru-Martínez, Roque

    2011-03-01

    The 4-plex iTRAQ platform was utilized to analyze the protein profiles in four stages of grapevine berry skin ripening, from pre-veraison to fully ripening. Mass spectrometric data were acquired from three replicated analyses using a parallel acquisition method in an Orbitrap instrument by combining collision-induced dissociation (CID) and higher energy collision-induced dissociation (HCD) peptide ion fragmentations. As a result, the number of spectra suitable for peptide identification (either from CID or HCD) increased 5-fold in relation to those suitable for quantification (from HCD). Spectra were searched against an NCBInr protein database subset containing all the Vitis sequences, including those derived from whole genome sequencing. In general, 695 unique proteins were identified with more than one single peptide, and 513 of them were quantified. The sequence annotation and GO term enrichment analysis assisted by the automatic annotation tool Blast2GO permitted a pathway analysis which resulted in finding that biological processes and metabolic pathways de-regulated throughout ripening. A detailed analysis of the function-related proteins profiles helped discover a set of proteins of known Vitis gene origin as the potential candidates to play key roles in grapevine berry quality, growth regulation and disease resistance.

  15. Study on water-dispersible colloids in saline-alkali soils by atomic force microscopy and spectrometric methods.

    Science.gov (United States)

    Liu, Zhiguo; Xu, Fengjie; Zu, Yuangang; Meng, Ronghua; Wang, Wenjie

    2016-06-01

    Recent studies have revealed that water-dispersible colloids play an important role in the transport of nutrients and contaminants in soils. In this study, water-dispersible colloids extracted from saline-alkali soils have been characterized by atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV absorption spectra. AFM observation indicated that the water-dispersible colloids contain some large plates and many small spherical particles. XRD, XPS, and UV absorption measurement revealed that the water-dispersible colloids are composed of kaolinite, illite, calcite, quartz and humic acid. In addition, UV absorption measurement demonstrated that the humic acids are associated with clay minerals. Water-dispersible colloids in the saline-alkali soils after hydrolyzed polymaleic anhydride treatment and an agricultural soil (nonsaline-alkali soil) were also investigated for comparison. The obtained results implied that the saline-alkali condition facilitates the formation of a large quantity of colloids. The use of AFM combined with spectrometric methods in the present study provides new knowledge on the colloid characteristics of saline-alkali soils. Microsc. Res. Tech. 79:525-531, 2016. © 2016 Wiley Periodicals, Inc.

  16. Interaction of norfloxacin with bovine serum albumin studied by different spectrometric methods; displacement studies, molecular modeling and chemometrics approaches

    Energy Technology Data Exchange (ETDEWEB)

    Naseri, Abdolhossein, E-mail: a_naseri@tabrizu.ac.ir [Departments of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 51666-16471 (Iran, Islamic Republic of); Hosseini, Soheila [Departments of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 51666-16471 (Iran, Islamic Republic of); Rasoulzadeh, Farzaneh [Drug Applied Research Center, Tabriz University of Medical Sciences, Tabriz 51644-14766 (Iran, Islamic Republic of); Rashidi, Mohammad-Reza [Research Center for Pharmaceutical Nanotechnology, Tabriz University of Medical Sciences, Tabriz 51644-14766 (Iran, Islamic Republic of); Zakery, Maryam; Khayamian, Taghi [Department of Chemistry, College of Chemistry, Isfahan University of Technology, Isfahan 84154 (Iran, Islamic Republic of)

    2015-01-15

    Serum albumins as major target proteins can bind to other ligands leading to alteration of their pharmacological properties. The mechanism of interaction between norfloxacin (NFLX) with bovine serum albumin (BSA) was investigated. Fuorescence quenching of serum albumin by this drug was found to be a static quenching process. The binding sites number, n, apparent binding constant, K, and thermodynamic parameters were calculated at different temperatures. The distance, r, between donor, BSA, and acceptor, NFLX, was calculated according to the Forster theory of non-radiation energy transfer. Also binding characteristics of NFLX with BSA together with its displacement from its binding site by kanamycin and effect of common metal ions on binding constant were investigated by the spectroscopic methods. The conformational change in the secondary structure of BSA upon interaction with NFLX was investigated qualitatively from synchronous fluorescence spectra, Fourier Transform Infrared (FTIR) and circular dichroism (CD) spectrometric methods. Molecular docking studies were performed to obtain information on the possible residues involved in the interaction process and changes in accessible surface area of the interacting residues. The results showed that the conformation of BSA changed in the presence of NFLX. For the first time, displacement studies were used for this interaction; displacement studies showed that NFLX was displaced by phenylbutazon and ketoprofen but was not displaced by ibuprofen indicating that the binding site of NFLX on albumin was site I. In addition a powerful chemometrics method, multivariate curve resolution-alternating least square, was used for resolution of spectroscopic augmented data obtained in two different titration modes in order to extract spectral information regardless of spectral overlapping of components. - Highlights: • Interaction between norfloxacin and BSA is studied by spectral methods. • Chemometrics methods are used to

  17. Spectrometric techniques 2

    CERN Document Server

    Vanasse, George A

    2013-01-01

    Spectrometric Techniques, Volume II provides information pertinent to vacuum ultraviolet techniques to complete the demonstration of the diversity of methods available to the spectroscopist interested in the ultraviolet visible and infrared spectral regions. This book discusses the specific aspects of the technique of Fourier transform spectroscopy.Organized into five chapters, this volume begins with an overview of the large number of systematic effects in the recording of an interferogram. This text then examines the design approach for a Fourier transform spectrometer with focus on optics.

  18. Differentiation of Aurantii Fructus Immaturus from Poniciri Trifoliatae Fructus Immaturus using flow-injection mass spectrometric (FIMS) metabolic fingerprinting method combined with chemometrics.

    Science.gov (United States)

    Zhao, Yang; Chang, Yuan-Shiun; Chen, Pei

    2015-03-25

    A flow-injection mass spectrometric metabolic fingerprinting method in combination with chemometrics was used to differentiate Aurantii Fructus Immaturus from its counterfeit Poniciri Trifoliatae Fructus Immaturus. Flow-injection mass spectrometric (FIMS) fingerprints of 9 Aurantii Fructus Immaturus samples and 12 Poniciri Trifoliatae Fructus Immaturus samples were acquired and analyzed using principal component analysis (PCA) and soft independent modeling of class analogy (SIMCA). The authentic herbs were differentiated from their counterfeits easily. Eight characteristic components which were responsible for the differences between the samples were tentatively identified. Furthermore, three out of the eight components, naringin, hesperidin, and neohesperidin, were quantified. The results are useful to help identify the authenticity of Aurantii Fructus Immaturus.

  19. Renewal of an old European Pharmacopoeia method for Terazosin using modeling with mass spectrometric peak tracking.

    Science.gov (United States)

    Kormány, Róbert; Molnár, Imre; Fekete, Jenő

    2017-02-20

    An older method for terazosin was reworked in order to reduce the analysis time from 90min (2×45min) to below 5min. The method in European Pharmacopoeia (Ph.Eur.) investigates the specified impurities separately. The reason of the different methods is that the retention of two impurities is not adequate in reversed phase, not even with 100% water. Therefore ion-pair-chromatography has to be applied and since that two impurities absorb at low UV-wavelength they had to be analyzed by different method than the other specified impurities. In our new method we could improve the retention with pH elevation using a new type of stationary phases available for high pH applications. Also a detection wavelength could be selected that is appropriate for the detection and quantification of all impurities. The method development is the bottleneck of liquid chromatography even today, when more and more fast chromatographic systems are used. Expert knowledge with intelligent programs is available to reduce the time of method development and offer extra information about the robustness of the separation. Design of Experiments (DoE) for simultaneous optimization of gradient time (tG), temperature (T) and ternary eluent composition (tC) requires 12 experiments. A good alternative way to identify a certain peak in different chromatograms is the molecular mass of the compound, due to its high specificity. Liquid Chromatography-Mass Spectrometry (LC-MS) is now a routine technique and increasingly available in laboratories. In our experiment for the resolution- and retention modeling the DryLab4 method development software (Version 4.2) was used. In recent versions of the software the use of (m/z)-MS-data is possible along the UV-peak-area-tracking technology. The modelled and measured chromatograms showed excellent correlations. The average retention time deviations were ca. 0.5s and there was no difference between the predicted and measured Rs,crit -values.

  20. Development of a Mass Spectrometric Method for Pharmacokinetic Study of Trastuzumab

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Nam Young; Choi, Jin Nyoung; Kang, Jeong Won; Choi, Do Young; Kim, Kwang Pyo [Kyung Hee Univ., Yongin (Korea, Republic of); Park, Gyutae [CKD Research Institute, Yongin (Korea, Republic of)

    2014-06-15

    The HPLC-MS/MS method described here is a simple, rapid and specific method for determining the concentration of biologics in mouse serum. This method was validated for the quantification trastuzumab in ICR mice serum. Although the ELISA method is available for the pharmacokinetics study for trastuzumab, but these methods require development of the target specific antibodies. Generally, the development of the target specific antibodies for quantification is time consuming and expensive. In contrast, MRM-based method does not need antibodies for quantification. The therapeutic monoclonal antibody drug Trastuzumab (INN; trade name Herceptin) is widely used for treating metastatic breast cancer patients with overexpression of HER2 on the tumor. Trastuzumab is a representative target therapeutics as a monoclonal antibody that selectively binds with high affinity to the extracellular domain of the human epidermal growth factor receptor 2 protein, HER2. HER2 is amplified or over-expressed in about 20% to 30% of patients with breast cancer and is associated with aggressive disease. Trastuzumab has an inhibitory effect on the overexpression of HER2 receptor, thereby it has been used in treating breast cancer, and also gastric cancer.

  1. DEVELOPMENT AND VALIDATION OF UV-VISIBLE SPECTROMETRIC METHOD FOR ESTIMATION OF WATER SOLUBLE VITAMIN RIBOFLAVIN

    Directory of Open Access Journals (Sweden)

    Himanshi Shah et al

    2012-09-01

    Full Text Available The present study describes a simple, accurate, precise and cost effective UV-Visible spectrophotometric method for the estimation of Riboflavin raw material. The Riboflavin is water soluble vitamin, so the solvent used throughout the experiment was 0.1N NaOH, the absorption maxima of drug was found at 445 nm. Beer’s law was obeyed in the range of 5ppm-30ppm. the developed method was successfully validated with respect to linearity, accuracy and precision. The method was validated and shown linearity in mentioned concentration. The correlation coefficient for Riboflavin was 0.999. The percentage relative standard deviation of inter-day precision range 0.66-1.04% and intra-day precision 1.05-1.39% both should be less than 2%. Hence proposed method was precise, accurate and cost effective, simple and rapid. This validated method can be applicable for quantitative determination of the titled drug with respect to assay from or for their solid dosage forms.

  2. Determination of total body water by a simple and rapid mass spectrometric method.

    Science.gov (United States)

    Van Kreel, B K; Van der Vegt, F; Meers, M; Wagenmakers, T; Westerterp, K; Coward, A

    1996-01-01

    A rapid and inexpensive method was developed to determine deuterium enrichment in body fluids. This is achieved by converting water into acetylene. To vacutainer tubes a small amount of calcium carbide is added. The tubes are evacuated and 25 microliters of sample are injected through the stopper. The reaction takes place spontaneously at room temperature in a few seconds. Enrichment at mass 27 compared with mass 26 can be determined by continuous flow isotope ratio mass spectrometry without any interference from the carrier gas helium. A series of D2O samples diluted with increasing amounts of H2O is prepared at the time of measurement of the biological samples and the measured ratios are used to calculate the isotope dilution of the unknown. The relative error of the method is 1.6% when a dose of 25 ml kg-1 is administered to the patient. The method was compared with two different methods in use in other laboratories, by a published method The means of the differences were -0.1 and 0.08 1, respectively, with standard deviations of 0.63 and 3.0.

  3. Atomic Absorption Spectrometric Method for Estimation of Diclofenac sodium and Mefenamic acid in Pharmaceutical Formulations

    Directory of Open Access Journals (Sweden)

    Sunil Jawla

    2010-01-01

    Full Text Available Diclofenac sodium and Mefenamic acid have been quantified in tablet dosage form by atomic absorption spectrometry (AAS. These methods are based on formation of the metal complexes of Diclofenac sodium and Mefenamic acid with cupric chloride and cobaltous chloride. The first method is based on reaction of both the drugs with cupric chloride to give light blue colored metal complexes, which are then extracted with dichloromethane and digested with 0.1 M nitric acid. Both the drugs are indirectly estimated via determination of copper content in the formed complexes by AAS. The second method is based on the formation of pink colored complexes of both the drugs with cobaltous chloride. These metal complexes are extracted with dichloromethane and estimated via determination of cobalt content in the formed complexes after digestion with 0.1 M nitric acid by AAS.

  4. A Mass Spectrometric Analysis Method Based on PPCA and SVM for Early Detection of Ovarian Cancer.

    Science.gov (United States)

    Wu, Jiang; Ji, Yanju; Zhao, Ling; Ji, Mengying; Ye, Zhuang; Li, Suyi

    2016-01-01

    Background. Surfaced-enhanced laser desorption-ionization-time of flight mass spectrometry (SELDI-TOF-MS) technology plays an important role in the early diagnosis of ovarian cancer. However, the raw MS data is highly dimensional and redundant. Therefore, it is necessary to study rapid and accurate detection methods from the massive MS data. Methods. The clinical data set used in the experiments for early cancer detection consisted of 216 SELDI-TOF-MS samples. An MS analysis method based on probabilistic principal components analysis (PPCA) and support vector machine (SVM) was proposed and applied to the ovarian cancer early classification in the data set. Additionally, by the same data set, we also established a traditional PCA-SVM model. Finally we compared the two models in detection accuracy, specificity, and sensitivity. Results. Using independent training and testing experiments 10 times to evaluate the ovarian cancer detection models, the average prediction accuracy, sensitivity, and specificity of the PCA-SVM model were 83.34%, 82.70%, and 83.88%, respectively. In contrast, those of the PPCA-SVM model were 90.80%, 92.98%, and 88.97%, respectively. Conclusions. The PPCA-SVM model had better detection performance. And the model combined with the SELDI-TOF-MS technology had a prospect in early clinical detection and diagnosis of ovarian cancer.

  5. A Mass Spectrometric Analysis Method Based on PPCA and SVM for Early Detection of Ovarian Cancer

    Directory of Open Access Journals (Sweden)

    Jiang Wu

    2016-01-01

    Full Text Available Background. Surfaced-enhanced laser desorption-ionization-time of flight mass spectrometry (SELDI-TOF-MS technology plays an important role in the early diagnosis of ovarian cancer. However, the raw MS data is highly dimensional and redundant. Therefore, it is necessary to study rapid and accurate detection methods from the massive MS data. Methods. The clinical data set used in the experiments for early cancer detection consisted of 216 SELDI-TOF-MS samples. An MS analysis method based on probabilistic principal components analysis (PPCA and support vector machine (SVM was proposed and applied to the ovarian cancer early classification in the data set. Additionally, by the same data set, we also established a traditional PCA-SVM model. Finally we compared the two models in detection accuracy, specificity, and sensitivity. Results. Using independent training and testing experiments 10 times to evaluate the ovarian cancer detection models, the average prediction accuracy, sensitivity, and specificity of the PCA-SVM model were 83.34%, 82.70%, and 83.88%, respectively. In contrast, those of the PPCA-SVM model were 90.80%, 92.98%, and 88.97%, respectively. Conclusions. The PPCA-SVM model had better detection performance. And the model combined with the SELDI-TOF-MS technology had a prospect in early clinical detection and diagnosis of ovarian cancer.

  6. A mass spectrometric method to determine activities of enzymes involved in polyamine catabolism

    Energy Technology Data Exchange (ETDEWEB)

    Moriya, Shunsuke; Iwasaki, Kaori [Department of Molecular Medicine, Tokyo Metropolitan Institute of Medical Science, 2-1-6 Kami-kitazawa, Setagaya-ku, Tokyo 156-8506 (Japan); Samejima, Keijiro, E-mail: samejima-kj@igakuken.or.jp [Department of Molecular Medicine, Tokyo Metropolitan Institute of Medical Science, 2-1-6 Kami-kitazawa, Setagaya-ku, Tokyo 156-8506 (Japan); Takao, Koichi [Faculty of Pharmaceutical Sciences, Josai University, 1-1 Keyakidai, Sakado, Saitama 350-0295 (Japan); Kohda, Kohfuku [Research Institute of Pharmaceutical Sciences, Musashino University, 1-1-20 Shinmachi, Nishitokyo, Tokyo 202-8585 (Japan); Hiramatsu, Kyoko; Kawakita, Masao [Department of Molecular Medicine, Tokyo Metropolitan Institute of Medical Science, 2-1-6 Kami-kitazawa, Setagaya-ku, Tokyo 156-8506 (Japan)

    2012-10-20

    Highlights: Black-Right-Pointing-Pointer Compounds in polyamine catabolic pathway were determined by a column-free ESI-TOF MS. Black-Right-Pointing-Pointer N{sup 1}- and N{sup 8}-acetylspermidine were determined by a column-free ESI-MS/MS. Black-Right-Pointing-Pointer The method was applied to determine activities of APAO, SMO, and SSAT in the pathway. Black-Right-Pointing-Pointer The assay method contained stable isotope-labeled natural substrates. Black-Right-Pointing-Pointer It is applicable to biological samples containing natural substrate and product. - Abstract: An analytical method for the determination of three polyamines (putrescine, spermidine, and spermine) and five acetylpolyamines [N{sup 1}-acetylspermidine (N{sup 1}AcSpd), N{sup 8}-acetylspermidine (N{sup 8}AcSpd), N{sup 1}-acetylspermine, N{sup 1},N{sup 8}-diacetylspermidine, and N{sup 1},N{sup 12}-diacetylspermine] involved in the polyamine catabolic pathway has been developed using a hybrid tandem mass spectrometer. Heptafluorobutyryl (HFB) derivatives of these compounds and respective internal standards labeled with stable isotopes were analyzed simultaneously by TOF MS, based on peak areas appearing at appropriate m/z values. The isomers, N{sup 1}AcSpd and N{sup 8}AcSpd were determined from their fragment ions, the acetylamidopropyl and acetylamidobutyl groups, respectively, using MS/MS with {sup 13}C{sub 2}-N{sup 1}AcSpd and {sup 13}C{sub 2}-N{sup 8}AcSpd which have the {sup 13}C{sub 2}-acetyl group as an internal standard. The TOF MS method was successfully applied to measure the activity of enzymes involved in polyamine catabolic pathways, namely N{sup 1}-acetylpolyamine oxidase (APAO), spermine oxidase (SMO), and spermidine/spermine N{sup 1}-acetyltransferase (SSAT). The following natural substrates and products labeled with stable isotopes considering the application to biological samples were identified; for APAO, [4,9,12-{sup 15}N{sub 3}]-N{sup 1}-acetylspermine and [1,4,8-{sup 15}N{sub 3

  7. Identification and quantification of adulteration in Garcinia cambogia commercial products by chromatographic and spectrometric methods.

    Science.gov (United States)

    Jamila, Nargis; Choi, Ji Yeon; Hong, Joon Ho; Nho, Eun Yeong; Khan, Naeem; Jo, Cheon Ho; Chun, Hyang Sook; Kim, Kyong Su

    2016-12-01

    Species of genus Garcinia are rich sources of bioactive constituents with antimicrobial, anticancer, anti-inflammatory, hepatoprotective and anti-HIV activities. Commercial products of Garcinia cambogia are used as anti-obesity drugs with increasing market demand. Because of the high price of its products, it can be adulterated with similar lower-priced species. This study was designed to develop and validate an accurate and efficient method for the detection of any adulteration (G. indica) in G. cambogia products. For this purpose, high performance liquid chromatography (HPLC) was used to analyse the ethanolic fruit rind extracts of G. cambogia and G. indica, their formulations of 0.5, 1, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 and 95% G. indica with G. cambogia, and 11 G. cambogia commercial products. The analytical methods were validated by quality assurance parameters of linearity, sensitivity, precision and accuracy. Two marker peaks were detected in G. indica fruit extract, whereas G. cambogia did not show these peaks. The detected peaks were identified as anthocyanins; cyanidin-3-O-sambubioside and cyanidin-3-O-glucoside. In the study to determine the effect of pH and temperature on the stability of its anthocyanin content, HPLC analysis of G. indica extract showed the highest content at pH 1 and 50°C. Using two different mobile phases, the limits of detection (LOD) for cyanidin-3-O-sambubioside and cyanidin-3-O-glucoside were 0.036 and 0.059, and 0.022 and 0.033 mg kg(-1), respectively. Furthermore, the inter-day precision (cambogia products is rapid and accurate.

  8. Application of Gas Chromatograph-Mass Spectrometry in Gun-Powder Analysis%气相色谱-质谱联用法在火药剖析中的应用

    Institute of Scientific and Technical Information of China (English)

    李俊平; 崔桂萍; 李彩青; 任洁; 梁瑞红

    2012-01-01

    采用固液萃取的方法对火药样品进行处理,用气相色谱-质谱联用法对某未知火药进行成分剖析,以选择离子质谱法进行定量.目标化合物浓度在20~50 mg/L范围内与色谱峰面积呈良好的线性关系,相关系数在0.9940~0.9996之间.方法加标回收率为96.9%~ 104.3%,测定结果的相对标准偏差为2.4%~4.9%(n=5).气相色谱-质谱联用法可用于火药剖析研究.%The gun-powder sample was treated by solid-liquid extraction method, the components in unknown gun-powder were anatomized by gas chromatograph-mass spectrometry. Selective ion quantitativis method was used for quantitative analysis. The concentration of target compound was linear with chromatographic peak area in the range of 20-50 mg/L, the correlation coefficient was 0.9940-0.9996. The recovery rate was 96.9%-104.3% and relative standard deviation of analysis results was 0.4%-4.9%(n=5). Gas chromatograph-mass spectrometry is suitable for the analysis of gun-powder anatomy research.

  9. Determination of organic chemicals in human whole blood: preliminary method development for volatile organics

    Energy Technology Data Exchange (ETDEWEB)

    Cramer, P.H.; Boggess, K.E.; Hosenfeld, J.M.; Remmers, J.C.; Breen, J.J.; Robinson, P.E.; Stroup, C.

    1988-04-01

    This article introduces a method for the detection and confirmation of selected volatile organics at parts-per-trillion (ppt) levels in whole human blood. Intended for routine use, the method consists of a dynamic headspace purge of water-diluted blood where a carrier gas sweeps the surface of the sample and removes a quantifiable amount of the volatile organics from the blood and into an adsorbent trap. The organics are thermally desorbed form the adsorbent trap and onto the analytical column in a gas-chromatographic/mass-spectrometric (GC/MS) system where limited mass-scan data are taken for qualitative and quantitative identification. The method can be employed for compounds normally defined as volatile organics, such as those on the EPA priority-pollutant-volatiles list. Method validation results and limited population-survey results are also presented here.

  10. Visual and light scattering spectrometric method for the detection of melamine using uracil 5‧-triphosphate sodium modified gold nanoparticles

    Science.gov (United States)

    Liang, Lijiao; Zhen, Shujun; Huang, Chengzhi

    2017-02-01

    A highly selective method was presented for colorimetric determination of melamine using uracil 5‧-triphosphate sodium modified gold nanoparticles (UTP-Au NPs) in this paper. Specific hydrogen-bonding interaction between uracil base (U) and melamine resulted in the aggregation of AuNPs, displaying variations of localized surface plasmon resonance (LSPR) features such as color change from red to blue and enhanced localized surface plasmon resonance light scattering (LSPR-LS) signals. Accordingly, the concentration of melamine could be quantified based on naked eye or a spectrometric method. This method was simple, inexpensive, environmental friendly and highly selective, which has been successfully used for the detection of melamine in pretreated liquid milk products with high recoveries.

  11. Performance characterization of a quantitative liquid chromatography-tandem mass spectrometric method for 12 macrolide and lincosamide antibiotics in salmon, shrimp and tilapia.

    Science.gov (United States)

    Dickson, Leslie C

    2014-09-15

    This paper describes an extension and performance characterization of a quantitative confirmatory multi-residue liquid chromatography-tandem mass spectrometric method for residues of macrolide and lincosamide antibiotics, originally validated for application to bovine kidney tissues, to tissues of salmon, shrimp and tilapia. The 12 analytes include clindamycin, erythromycin A, gamithromycin, josamycin, lincomycin, neospiramycin 1, oleandomycin, pirlimycin, spiramycin 1, tildipirosin, tilmicosin and tylosin A. The limit of detection was 0.5 μg/kg. Within-laboratory precision evaluated over the analytical range of 5.0-50.0 μg/kg ranged from 4 to 17%. The accuracy of the method ranged from 80 to 112%. Recoveries ranged from 47 to 99% with all but one recovery above 60%. This is the first report of a quantitative confirmatory method for gamithromycin, pirlimycin and tildipirosin in fish and shrimp.

  12. Standard test methods for chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade mixed oxides ((U, Pu)O2)

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2010-01-01

    1.1 These test methods cover procedures for the chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade mixed oxides, (U, Pu)O2, powders and pellets to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Uranium in the Presence of Pu by Potentiometric Titration Plutonium by Controlled-Potential Coulometry Plutonium by Amperometric Titration with Iron (II) Nitrogen by Distillation Spectrophotometry Using Nessler Reagent 7 to 14 Carbon (Total) by Direct Combustion-Thermal Conductivity 15 to 26 Total Chlorine and Fluorine by Pyrohydrolysis 27 to 34 Sulfur by Distillation-Spectrophotometry 35 to 43 Moisture by the Coulometric, Electrolytic Moisture Analyzer 44 to 51 Isotopic Composition by Mass Spectrometry Rare Earths by Copper Spark Spectroscopy 52 to 59 Trace Impurities by Carrier Distillation Spectroscopy 60 to 69 Impurities by Spark-Source Mass Spectrography 70 to 76 Total Gas in Reactor-Grade Mixed Dioxide P...

  13. Spectrometric techniques 3

    CERN Document Server

    Vanasse, George A

    2013-01-01

    Spectrometric Techniques, Volume III presents the applications of spectrometric techniques to atmospheric and space studies. This book reviews the spectral data processing and analysis techniques that are of broad applicability.Organized into five chapters, this volume begins with an overview of the instrumentation used for obtaining field data. This text then reviews the contribution that space-borne spectroscopy in the thermal IR has made to the understanding of the planets. Other chapters consider the instruments that have recorded the planetary emission spectra. This book discusses as well

  14. Validation of method for determination of different classes of pesticides in aqueous samples by dispersive liquid-liquid microextraction with liquid chromatography-tandem mass spectrometric detection.

    Science.gov (United States)

    Caldas, Sergiane Souza; Costa, Fabiane Pinho; Primel, Ednei Gilberto

    2010-04-14

    In this study, a simple, rapid and efficient method has been developed for the extraction and preconcentration of different classes of pesticides, carbofuran (insecticide), clomazone (herbicide) and tebuconazole (fungicide) in aqueous samples by dispersive liquid-liquid microextraction (DLLME) coupled with liquid chromatography-tandem mass spectrometric detection. Some experimental parameters that influence the extraction efficiency, such as the type and volume of the disperser solvents and extraction solvents, extraction time, speed of centrifugation, pH and addition of salt were examined and optimized. Under the optimum conditions, the recoveries of pesticides in water at spiking levels between 0.02 and 2.0 microg L(-1) ranged from 62.7% to 120.0%. The relative standard deviations varied between 1.9% and 9.1% (n=3). The limits of quantification of the method considering a 50-fold preconcentration step were 0.02 microg L(-1). The linearity of the method ranged from 1.0 to 1000 microg L(-1) for all compounds, with correlation coefficients varying from 0.9982 to 0.9992. Results show that the method we propose can meet the requirements for the determination of pesticides in water samples. The comparison of this method with solid-phase extraction indicates that DLLME is a simple, fast, and low-cost method for the determination of pesticides in natural waters.

  15. 环境空气中尼古丁的气相色谱-质谱测定法%Determination of Environmental Air Nicotine by Gas Chromatograph-Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    董小艳; 王秦; 徐东群

    2011-01-01

    目的 采用被动式采样器采样,气相色谱-质谱法测定环境空气中尼古丁.方法 环境空气中的尼古丁用经过NaHS04处理过的玻璃纤维滤膜采集,滤膜经1.5 mol/L NaOH洗脱和正庚烷萃取后经气相色谱分离,采用质谱选择离子扫描方式采集数据,保留时间和特征离子定性,并以喹啉作为内标物进行定量.结果 该方法的检出限为0.01 μg/ml,定量下限0.034μg/ml,按采样体积312 L计,线性范围为0.22~16μg/m3.低、中、高3个浓度的标准溶液6次测定的RSD分别为8.4%,6.0%和4.9%;3个浓度的加标回收率范围分别为82.8%~97.4%,94.0%~109.8%和85.4%-109.8%.结论 本方法采样方便,测定灵敏、准确,可以在场所监测或人群个体暴露环境烟草烟雾(ETS)监测中大规模使用,为客观评价ETS暴露提供技术手段.%Objective To establish a method for the determination of environmental air nicotine by passive diffusion sampling and chromatograph-mass spectrometry analysis. Methods The environmental air nicotine was collected onto the filter treated with sodium bisulfate by diffusing first, and then desorbed and extracted into the solution of 1.5 mol/L sodium hydroxide and heptane from the filter, the nicotine in the heptane was analyzed by gas chromatograph-mass spectrometry with SIM (selected ion monitoring), quinoline was used as internal standard to quantitative analysis. Results The limit of detection was 0.01 μg/ml and the limit of quantification was 0.034 μg/ml, the linear range of the method was 0.22-16 μg/m3 with 312 L sampling volume, the relative standard deviations of three levels concentrations were 8.4%, 6.0% and 4.9% respectively, and the recovery range of three levels concentrations were 82.8%-97.4%,94.0%-109.8% and 85.4%-109.8% respectively. Conclusion The method is convenient with the passive sampling, sensitive and accurate with gas chromatograph-mass spectrometry, it can be used in field study for

  16. Determination of hexanal as an oxidative marker in vegetable oils using an automated dynamic headspace sampler coupled to a gas chromatograph/mass spectrometer.

    Science.gov (United States)

    Ha, Jaeho; Seo, Dong-Won; Chen, Xi; Hwang, Jin-Bong; Shim, You-Shin

    2011-01-01

    An automated dynamic headspace sampler coupled to a gas chromatograph/mass spectrometer was evaluated as an oxidative marker to determine hexanal content in vegetable oils. For the effective analysis, a cooled injection system (CIS) was used to focus and to introduce the hexanal desorbed from the Tenax TA. The temperature of the CIS was maintained at -60 °C for 12 min before desorbing the hexanal. Hexanal was separated on a capillary column (DB-5, 0.25 mm × 60 m, 0.25 µm in film thickness) from 50 to 230 °C, followed by mass spectrometer-selected ion monitoring analysis at m/z 56. The instrumental response to hexanal was highly linear from 10 ng mL(-1) to 1 µg mL(-1) (r(2) = 0.9999). The relative standard deviation (RSD) of intra- and inter-day repeatability was acceptable, with values of less than 3.88 and 4.25%, respectively. The LOD and LOQ of hexanal were determined by gas chromatograph/mass spectrometer-selected ion monitoring to be 3.3 and 9.8 ng mL(-1), respectively. The acid value, peroxide value and fatty acid composition revealed a good correlation with the hexanal concentration.

  17. Parallel development of chromatographic and mass-spectrometric methods for quantitative analysis of glycation on an IgG1 monoclonal antibody.

    Science.gov (United States)

    Viski, Kornél; Gengeliczki, Zsolt; Lenkey, Krisztián; Baranyáné Ganzler, Katalin

    2016-10-01

    Monitoring post-translational modifications (PTMs) in biotherapeutics is of paramount importance. In pharmaceutical industry, chromatography with optical detection is the standard choice of quantitation of product related impurities; and mass spectrometry is used only for characterization. Parallel development of a boronate affinity chromatographic (BAC) and a mass spectrometric methods for quantitative measurement of glycation on a monoclonal antibody (mAb) shed light on the importance of certain characteristics of the individual methods. Non-specific interactions in BAC has to be suppressed with the so-called shielding reagent. We have found that excessive amount of shielding reagents in the chromatographic solvents may cause significant underestimation of glycation. Although contamination of the retained peak with the non-glycated isoforms in BAC is unavoidable, our work shows that it can be characterized and quantitated by mass spectrometry. It has been demonstrated that glycation can be measured by mass spectrometry at the intact protein level with an LOQ value of 3.0% and error bar of ±0.5%. The BAC and MS methods have been found to provide equivalent results. These methods have not been compared from these points of view before.

  18. A liquid chromatography-atmospheric pressure photoionization tandem mass spectrometric method for the determination of organosulfur compounds in petroleum asphalt cements.

    Science.gov (United States)

    da Silveira, Géssica Domingos; Faccin, Henrique; Claussen, Luis; Goularte, Rayane Bueno; Do Nascimento, Paulo C; Bohrer, Denise; Cravo, Margareth; Leite, Leni F M; de Carvalho, Leandro Machado

    2016-07-29

    We present a sensitive liquid chromatography-atmospheric pressure photoionization tandem mass spectrometric (UHPLC-APPI-MS/MS) method for the determination of selected organosulfur compounds in Brazilian asphalt cements. It was possible to detect 14 organosulfur compounds of different classes where sulfoxides and sulfones presented higher sensibility in ionization than thiophenes and aromatic sulfides. A dopant-assisted APPI method was also tested, however, when chromatographic flow rate was optimized a decrease in signal was observed for all compounds. PAHs were tested and ruled out as possible interfering compounds and the matrix effect of asphalt cements was within an acceptable range for the quantification of organosulfur compounds. The proposed method was found to have satisfactory linearity and accuracy with recoveries between 83.85 and 110.28% for thianaphthene and 3-methylbenzothiophene, respectively. Therefore, the method allowed the characterization of organosulfur compounds in Brazilian asphalt cements and demonstrated changes in the amount quantified in asphaltenic and maltenic fractions after the RTFOT+SUNTEST aging process.

  19. A method of test for residual isophorone diisocyanate trimer in new polyester-polyurethane coatings on light metal packaging using liquid chromatography with tandem mass spectrometric detection.

    Science.gov (United States)

    Driffield, Malcolm; Bradley, Emma L; Castle, Laurence

    2007-02-02

    A method of test for residual isophorone diisocyanate (IPDI) trimer in experimental formulation polyester-polyurethane (PEPU) thermoset coatings on metal food packaging is described. The method involves extraction of coated panels using acetonitrile containing dibutylamine for concurrent derivatisation, and then high performance liquid chromatography with electrospray ionisation tandem mass spectrometric detection (LC-MS/MS). Single laboratory validation was carried out using three different experimental PEPU-based coatings. The calibrations were linear, the analytical recovery was good, no interferences were seen, and substance identification criteria were met. The detection limit of the method is around 0.02 micro g/100 cm(2) of coating, which for a typical sized can and assuming complete migration of any residual IPDI trimer, corresponds to about 0.2 micro g/kg food or beverage. Separate studies indicated that, even if migration occurred at such low levels, the IPDI trimer would not be expected to persist in canned aqueous or fatty foodstuffs as it would hydrolyse to the corresponding aliphatic amine or react with food components to destroy the isocyanate moiety. The method of test developed here for residual IPDI trimer in thermoset polyester-polyurethane coatings should prove to be a valuable tool for investigating the cure kinetics of these novel coatings and help to guide the development of enhanced formulations.

  20. Standard test methods for chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade aluminum oxide and aluminum oxide-boron carbide composite pellets

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    1994-01-01

    1.1 These test methods cover procedures for the chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade aluminum oxide and aluminum oxide-boron carbide composite pellets to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Boron by Titrimetry 7 to 13 Separation of Boron for Mass Spectrometry 14 to 19 Isotopic Composition by Mass Spectrometry 20 to 23 Separation of Halides by Pyrohydrolysis 24 to 27 Fluoride by Ion-Selective Electrode 28 to 30 Chloride, Bromide, and Iodide by Amperometric Microtitrimetry 31 to 33 Trace Elements by Emission Spectroscopy 34 to 46 1.3 The values stated in SI units are to be regarded as the standard. 1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. (F...

  1. A multiresidue liquid chromatographic/tandem mass spectrometric method for the detection and quantitation of 15 nonsteroidal anti-inflammatory drugs (NSAIDs) in bovine meat and milk.

    Science.gov (United States)

    van Pamel, Els; Daeseleire, Els

    2015-06-01

    This study concerns a validated liquid chromatographic/tandem mass spectrometric (LC-MS/MS) multiresidue method for the simultaneous detection, identification, and quantitation of 15 nonsteroidal anti-inflammatory drugs (NSAIDs) in bovine meat and milk. The NSAIDs considered are carprofen, diclofenac, flufenamic acid, flunixin (5-hydroxyflunixin as marker metabolite in milk), ketoprofen, mefenamic acid, meloxicam, 4-methylaminoantipyrine (marker metabolite of metamizole in meat and milk), naproxen, niflumic acid, phenylbutazone (and metabolite oxyphenbutazone), ramifenazone, salicylic acid, and tolfenamic acid. These compounds were chosen as representatives of different chemical subclasses of NSAIDs. Flunixin-d3, diclofenac-d4, 4-aminoantipyrine-d3, and phenylbutazone-d10 were used as internal standards. Performance characteristics were validated according to the Commission Decision 2002/657/EC (Off J Eur Communities, L221: 8-36). Recovery percentages varied between 81 and 114% for bovine meat and between 79 and 118% for milk. Repeatability percentages were within the range of 1-12% for meat and between 1 and 17% for milk, whereas the intralaboratory reproducibility varied between 3 and 19% for meat and between 3 and 23% for milk. The decision limit and the detection capability for bovine meat were within the range of 0.5-579 μg kg(-1)and 0.6-642 μg kg(-1), respectively. Those for milk were within the range of 0.12-55 μg kg(-1) and 0.14-61 μg kg(-1), respectively. The methods developed were successfully applied for proficiency test samples and routine samples analyzed in the laboratory. The methodology concerns fast, user-friendly, and sensitive methods, which can be easily extended for other compounds and matrices. In general, such multiresidue methods contribute to the reduction of human exposure to these veterinary drug residues by consumption of contaminated bovine-derived products such as meat and milk.

  2. A liquid chromatography-tandem mass spectrometric method for quantitative determination of native 5-methyltetrahydrofolate and its polyglutamyl derivatives in raw vegetables.

    Science.gov (United States)

    Wang, Chao; Riedl, Ken M; Schwartz, Steven J

    2010-11-01

    Folate deficiency is a prevalent phenomenon worldwide especially in underprivileged countries. Polyglutamyl 5-methyltetrahydrofolate (5MTHF) species are the naturally occurring principle folate in store-bought vegetables. Here we report a simple and complete extraction method for the determination of native polyglutamyl 5-methyltetrahydrofolate in vegetables using high performance liquid chromatography with tandem mass spectrometric detection (HPLC-MS/MS). Coarsely chopped samples (18 different vegetables) were steamed to inactivate glutamylase enzymes and liberate folate from binding proteins and extracted in a reducing buffer with (13)C(5) 5MTHF stable isotope added as internal standard. The polyglutamyl 5-methyltetrahydrofolate species were separated in 9 min on a C(18) column using a reversed phase system. HPLC eluate was interfaced with a triple quadrupole mass spectrometer operated in electrospray positive mode. The respective pseudomolecular cation of each polyglutamyl 5-methyltetrahydrofolate species was selected for fragmentation to a common daughter ion for detection. We quantitated polyglutamyl 5-methyltetrahydrofolate in store-bought vegetables from families Brassicaceae, Asteraceae and Amaranthaceae (including mustard greens, romaine lettuce and Swiss chard) of which most have not been quantitated previously. Most vegetables from Asteraceae and those from Amaranthaceae contained similar amounts of monoglutamyl 5MTHF and polyglutamyl 5MTHF while Brassicaceae were dominated by polyglutamyls and endive species (Asteraceae) contained mainly monoglutamyl 5MTHF. The precision of the method for the various polyglutamyl 5-methyltetrahydrofolate forms was 1-9% RSD, recovery 84-91%, limit of detection 64-658 fmol and limit of quantitation 193-1994 fmol. Herein we describe a rapid, sensitive and selective HPLC-MS/MS technique to quantitate polyglutamyl 5-methyltetrahydrofolate species. This method may be suitable for analyzing the polyglutamyl 5

  3. An ultra-high-performance liquid chromatography-tandem mass spectrometric method for the determination of hederacoside C, a drug candidate for respiratory disorder, in rat plasma.

    Science.gov (United States)

    Rehman, Shaheed Ur; Choi, Min Sun; Kim, In Sook; Kim, Seung Hyun; Yoo, Hye Hyun

    2016-09-10

    Hederacoside C is a principal bioactive pharmaceutical ingredient of Hedera helix leaf extracts. H. helix extracts have long been used in folk medicine for the treatment of respiratory disorders. Currently, hederacoside C is investigated as a promising candidate for the treatment of respiratory diseases. In this study, an accurate, sensitive, rapid, and reliable bioanalytical method was developed for the determination of hederacoside C in rat plasma using ultra high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). For sample preparation, plasma proteins were precipitated with 0.1% acetic acid in acetonitrile. Waters UPLC BEH C18 (2.1mm I.D.×100mm, 1.7μm) column was used for chromatographic separation. A gradient elution of mobile phases consisting of 0.02% acetic acid in distilled water (solvent A) and 0.02% acetic acid in acetonitrile (solvent B) was used at a flow rate of 0.3mL/min. The multiple reaction monitoring (MRM) mode was used for mass spectrometric detection; the MRM transitions were m/z 1219.7→m/z 469.2 for hederacoside C and m/z 1108.3→m/z 221.2 for ginsenoside Rb1 (internal standard) in the negative ionization mode. A calibration curve was constructed in the range of 10-1000ng/mL. The intra- and inter-day precision and accuracy were within 5%. The developed UPLC-MS/MS method was successfully applied in a pharmacokinetic study of hederacoside C in rats. Hederacoside C was quickly but inadequately absorbed from the gastrointestinal tract of rats resulting in extremely low bioavailability and relatively slow clearance.

  4. Dynamic Cluster Analysis: An Unbiased Method for Identifying A+2 Element Containing Compounds in Liquid Chromatographic High-Resolution TOF Mass Spectrometric Data

    DEFF Research Database (Denmark)

    Andersen, Aaron John Christian; Hansen, Per Juel; Jørgensen, Kevin

    2016-01-01

    Dynamic Cluster Analysis (DCA) is an automated, unbiased technique which can identify Cl, Br, S, and other A+2 element containing metabolites in liquid chromatographic high resolution mass spectrometric data. DCA is based on three features, primarily the previously unutilised A+1 to A+2 isotope c...

  5. Radon tightness of different sample sealing methods for gamma spectrometric measurements of ²²⁶Ra.

    Science.gov (United States)

    Mauring, Alexander; Gäfvert, Torbjörn

    2013-11-01

    Different methods for sealing sample containers for (222)Rn when measuring (226)Ra through its progenies (214)Pb and (214)Bi using gamma-ray spectrometry have been investigated. Results show that a method consisting of vacuum packaging of the sample container in a sealed aluminium lined bag gives excellent results for ensuring radon tightness. However, care should be taken to fill the sample container completely in order to avoid systematic errors due to radon accumulating in the void volume.

  6. Measurement of quantity of iron in magnetically labeled cells: comparison among different UV/VIS spectrometric methods.

    Science.gov (United States)

    Rad, Ali M; Janic, Branislava; Iskander, A S M; Soltanian-Zadeh, Hamid; Arbab, Ali S

    2007-11-01

    Cell labeling with superparamagnetic iron oxides (SPIO) is becoming a routine procedure in cellular magnetic resonance imaging (MRI). Quantifying the intracellular iron in labeled cells is a prerequisite for determining the number of accumulated cells by quantitative MRI studies. To establish the most sensitive and reproducible method for measuring iron concentration in magnetically labeled cells, we investigated and compared four different methods using an ultraviolet-visible (UV/VIS) spectrophotometer. Background spectra were obtained for 5 and 10 M hydrochloric acids, a mixture of 100 mM citric acid plus ascorbic acid and bathophenanthroline sulphonate (BPS), and a mixture of 5 M hydrochloric acid plus 5% ferrocyanide. Spectra of the same solutions containing either 10 or 5 microg/mL iron oxides were also created to determine the peak absorbance wavelengths for the dissolved iron. In addition, different known iron concentrations were used to obtain calibration lines for each method. Based on the calibration factors, iron was measured in samples with a known amount of iron and in labeled cells. Methods based on the use of 10 M hydrochloric acid underestimated iron concentration in all experiments; for this method to give an accurate measurement, iron concentration in sample needs to be at least 3 microg/mL.

  7. Ultrahigh-performance liquid chromatographic-tandem mass spectrometric multimycotoxin method for quantitating 26 mycotoxins in maize silage.

    Science.gov (United States)

    Van Pamel, Els; Verbeken, Annemieke; Vlaemynck, Geertrui; De Boever, Johan; Daeseleire, Els

    2011-09-28

    A multianalyte method was developed to identify and quantitate 26 mycotoxins simultaneously in maize silage by means of ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The extraction and cleanup procedure consists of two extraction steps followed by purification on a Waters Oasis HLB column. The method developed was validated with the requirements of Commission Decision 2002/657/EC taken into account. The limit of detection and quantitation ranges were 5-348 and 11-695 ng/g, respectively. Apparent recovery varied between 61 and 116%, whereas repeatability and reproducibility were within the ranges of 3-45 and 5-49%, respectively. The method developed was successfully applied for maize silage samples taken at the cutting surface and 1 m behind that surface. Mainly Fusarium toxins (beauvericin, deoxynivalenol, enniatins, fumonisins, fusaric acid, and zearalenone) were detected, but postharvest toxins such as mycophenolic acid and roquefortine C were identified as well.

  8. Critical comparison of radiometric and mass spectrometric methods for the determination of radionuclides in environmental, biological and nuclear waste samples

    DEFF Research Database (Denmark)

    Hou, Xiaolin; Roos, Per

    2008-01-01

    spectrometry, and glow discharge mass spectrometry are reviewed for the determination of radionuclides. These methods are critically compared for the determination of long-lived radionuclides important for radiation protection, decommissioning of nuclear facilities, repository of nuclear waste, tracer...... application in the environmental and biological researches, these radionuclides include H-3, C-14, Cl-36, Ca-41 Ni-59,Ni-63, Sr-89,Sr-90, Tc-99, I-129, Cs-135,Cs-137, Pb-210, Ra-226,Ra-228, Np-237, Am-241, and isotopes of thorium, uranium and plutonium. The application of on-line methods (flow injection...

  9. An atomic absorption spectrometric method for the determination of phosphorus in foodstuffs using the bismuth phosphomolybdate complex

    Directory of Open Access Journals (Sweden)

    LJILJANA V. MIHAJLOVIC

    2000-06-01

    Full Text Available A new indirect AAS method using the bismuth phosphomolybdate complex for the determination of phosphorus in foodstuffs is suggested. The bismuth phosphomolybdate complex in acid medium was extacted with isobutyl methylketone and the phosphorus was determined through bismuth in an air/acetylene flame by utilising the 223.06 nm resonance line of bismuth. The interference caused by antimony and titanium can be neglected in the presence of excess of bismuth. The detection limit of the method is 0.008 mg/mL of phosphorus.

  10. Method development for liquid chromatographic/triple quadrupole mass spectrometric analysis of trace level perfluorocarboxylic acids in articles of commerce

    Science.gov (United States)

    An analytical method to identify and quantify trace levels of C5 to C12 perfluorocarboxylic acids (PFCAs) in articles of commerce (AOC) is developed and rigorously validated. Solid samples were extracted in methanol, and liquid samples were diluted with a solvent consisting of 60...

  11. Development of off-line layer chromatographic and total reflection X-ray fluorescence spectrometric methods for arsenic speciation

    Energy Technology Data Exchange (ETDEWEB)

    Mihucz, Victor G. [Joint Research Group of Environmental Chemistry of Hungarian Academy of Sciences and L. Eoetvoes University, P. O. Box 32, H-1518 Budapest (Hungary); Hungarian Satellite Centre of Trace Elements Institute to UNESCO, P. O. Box 32, H-1518 Budapest (Hungary); Moricz, Agnes M. [L. Eoetvoes University, Department of Chemical Technology and Environmental Chemistry, P.O. Box 32, H-1518 Budapest (Hungary); Kroepfl, Krisztina [Joint Research Group of Environmental Chemistry of Hungarian Academy of Sciences and L. Eoetvoes University, P. O. Box 32, H-1518 Budapest (Hungary); Szikora, Szilvia [Joint Research Group of Environmental Chemistry of Hungarian Academy of Sciences and L. Eoetvoes University, P. O. Box 32, H-1518 Budapest (Hungary); Tatar, Eniko [Hungarian Satellite Centre of Trace Elements Institute to UNESCO, P. O. Box 32, H-1518 Budapest (Hungary); L. Eoetvoes University, Department of Inorganic and Analytical Chemistry, P.O. Box 32, H-1518 Budapest (Hungary); Parra, Lue Meru Marco [Universidad Centro-occidental Lisandro Alvarado, Decanato de Agronomia, Departamento de Quimica y Suelos Unidad de Analisis Instrumental, Apartado Postal 4076, Cabudare 3023 (Venezuela); Zaray, Gyula [Joint Research Group of Environmental Chemistry of Hungarian Academy of Sciences and L. Eoetvoes University, P. O. Box 32, H-1518 Budapest (Hungary) and Hungarian Satellite Centre of Trace Elements Institute to UNESCO, P. O. Box 32, H-1518 Budapest (Hungary) and L. Eoetvoes University, Department of Inorganic and Analytical Chemistry, P.O. Box 32, H-1518 Budapest (Hungary)]. E-mail: zaray@ludens.elte.hu

    2006-11-15

    Rapid and low cost off-line thin layer chromatography-total reflection X-ray fluorescence spectrometry and overpressured thin layer chromatography-total reflection X-ray fluorescence spectrometry methods have been developed for separation of 25 ng of each As(III), As(V), monomethyl arsonic acid and dimethylarsinic acid applying a PEI cellulose stationary phase on plastic sheets and a mixture of acetone/acetic acid/water = 2:1:1 (v/v/v) as eluent system. The type of eluent systems, the amounts (25-1000 ng) of As species applied to PEI cellulose plates, injection volume, development distance, and flow rate (in case of overpressured thin layer chromatography) were taken into consideration for the development of the chromatographic separation. Moreover, a microdigestion method employing nitric acid for the As spots containing PEI cellulose scratched from the developed plates divided into segments was developed for the subsequent total reflection X-ray fluorescence spectrometry analysis. The method was applied for analysis of root extracts of cucumber plants grown in As(III) containing modified Hoagland nutrient solution. Both As(III) and As(V) were detected by applying the proposed thin layer chromatography/overpressured thin layer chromatography-total reflection X-ray fluorescence spectrometry methods.

  12. Standard test method for graphite furnace atomic absorption spectrometric determination of lead and cadmium extracted from ceramic foodware

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2000-01-01

    1.1 This test method covers procedures for using graphite furnace atomic absorption spectroscopy (GFAAS) to quantitatively determine lead and cadmium extracted by acetic acid at room temperature from the food-contact surface of foodware. The method is applicable to food-contact surfaces composed of silicate-based materials (earthenware, glazed ceramicware, decorated ceramicware, decorated glass, and lead crystal glass) and is capable of determining lead concentrations greater than 0.005 to 0.020 g/mL and cadmium concentrations greater than 0.0005 to 0.002 g/mL, depending on instrument design. 1.2 This test method also describes quality control procedures to check for contamination and matrix interference during GFAAS analyses and a specific sequence of analytical measurements that demonstrates proper instrument operation during the time period in which sample solutions are analyzed. 1.3 Cleaning and other contamination control procedures are described in this test method. Users may modify contamination cont...

  13. Simple mass spectrometric method for the estimation of boron and aluminum in water at the parts per billion level.

    Science.gov (United States)

    Krishnan, Nagasathiya; Raman, Pachaiappan; Mariappanadar, Vairamani

    2015-01-01

    The coordinating nature of the hydroxy carboxylic acids, such as tartaric and citric acids, has been utilized for the in-situ formation of anions representing the trivalent elements boron and aluminum and two dianions of the hydroxy acid selected under negative electrospray ionization mass spectral conditions. The abundance of these ions could be used for the quantification of boron and aluminum in water at concentrations ranging from 4.0 ppb to 535.0 ppb. For a period of six months, the validity of this method was tested with citric acid as the coordinating agent. Thus, the developed method offers a simple means for the quantification of boron and aluminum in water by negative electrospray ionization mass spectrometry with a single quadrupole mass spectrometer.

  14. OPTIMIZATION OF A UV-VIS SPECTROMETRIC METHOD FOR CAFFEINE ANALYSIS IN TEA, COFFEE AND OTHER BEVERAGES

    Directory of Open Access Journals (Sweden)

    S. DOBRINAS

    2014-01-01

    Full Text Available A method has been developed and validated for the determination of caffeine in tea, coffee and other beverages by UV-VIS spectrometry. A linear calibration curve was generated with caffeine concentration ranging from 3 mg∙L-1 to 18 mg∙L-1. The procedure developed provides a 0.85 mg∙L-1 detection limit of caffeine, respectively 1.52 mg∙L-1 quantification limit and the relative standard deviation (RSD was less than 0.05 % for independent measurement. The developed method was sensitive/specific and robust. Caffeine in tea infusions was found to be dependent on infusion time, the longer of the infusion time and the higher of the caffeine concentrations in tea infusions.

  15. Theory and Application of Mass Spectrometric Kinetic Method%质谱动力学方法原理及应用

    Institute of Scientific and Technical Information of China (English)

    李明; 李红梅; 熊行创; 江游; 黄泽建; 方向

    2012-01-01

    The mass spectrometric kinetic method based on the competitive dissociations of mass-selected cluster ions has been increasingly applied to thermochemical determination mainly due to its simplicity, speediness and sensitivity. Because the kinetic method employs tandem mass spectrometry, the compounds of interest need not be available in pure form. The kinetic method has been used to estimate gas-phase acidity and basicity and proton affinity, electron affinity, ionization energy, gas-phase basicities of multiply-charged biomole-cules, metal ion affinities, heterolytic bond dissociation energies, chiral recognition and quantification. In this paper the theory of kinetic method is introduced in detail and its applications are enumerated.%质谱动力学方法(Kinetic Method,简称KM法)是一种基于经质量选择的簇离子竞争解离反应速率的不同对热力学数据进行测定的方法,由于采用串联质谱技术,分析样品无需纯化,具有简便、快速、灵敏等优点.目前该方法已应用于气相酸碱度和质子亲合势的测定、电子亲和能的测定、电离能的测定、多电荷生物分子气相碱度的测定、金属离子与生物分子亲和力的测定、异裂离解能的测定、离子结构的检测及对手性化合物对映体过量的测定等.本工作在介绍质谱动力学方法原理的同时,列举了其应用实例,详细地对质谱动力学方法进行了综合述评.

  16. Development of a fast atom bombardment tandem mass spectrometric screening method for alkyl-ended oligomeric biguanides

    Science.gov (United States)

    Monaghan, J. J.; Morden, W. E.

    1992-12-01

    The FAB-MS and FAB-MS---MS behaviour of a series of "alkyl-ended" oligomeric biguanides has been studied. MS---MS product ion scans showed that fragmentation of these species occurred by predictable cleavages of the biguanide chains. Results are presented from a number of MS---MS precursor ion and neutral loss scans studied in an attempt to develop a screening method for biguanides in complex mixtures. The most effective of these scans is shown to be the neutral loss of the N-alkylguanidine molecule. Use of this scan is demonstrated for a mixture of oligomeric biguanides.

  17. Liquid Chromatography-Electrospray Quadrupole Linear Ion Trap Mass Spectrometric Method for Quantitation of Domperidone in Chinese Healthy Volunteers

    Institute of Scientific and Technical Information of China (English)

    WU Yi; CHU Yang; ZHANG Yun-hui; WU Dan; GU Jing-kai

    2007-01-01

    A rapid, sensitive, and accurate method based on LC/MS/MS was developed and validated for the determination of domperidone in human plasma. Domperidone and internal standard, tramadol, were extracted from plasma with diethyl ether-dichloromethane(60: 40, volume ratio) and separated by reversed-phase HPLC with methanol-water-ammonia solution(80: 20: 0.2, volume ratio) as the mobile phase. Detection was carried out via multiple-reaction monitoring(MRM) on a Q-trapTM LC/MS/MS system(Q-trapTM). The assay result was linear over a concentration range of 0.1-30 ng/mL with a limit of quantitation (LOQ) of 0.1 ng/mL. The inter- and intra-day precision levels were within 7.52% and 12. 9%, respectively, whereas the accuracy was within a range of 87. 3%-114%. This method has been successfully applied to evaluate the pharmacokinetics of domperidone in Chinese healthy volunteers given an oral dose of 10 mg.

  18. Development of a cloud point extraction and preconcentration method for Cd and Ni prior to flame atomic absorption spectrometric determination

    Energy Technology Data Exchange (ETDEWEB)

    Manzoori, Jamshid L. [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz (Iran, Islamic Republic of)]. E-mail: manzoori@tabrizu.ac.ir; Karim-Nezhad, Ghasem [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz (Iran, Islamic Republic of)

    2004-09-13

    In this work a new cloud point extraction (CPE) methodology was developed for the separation and preconcentration of cadmium and nickel. The analyte in the initial aqueous solution was complexed with dithizone and Triton X-114 was added as surfactant. After phase separation, based on the cloud point of the mixture, and dilution of the surfactant-rich phase with tetrahydrofuran (THF), the enriched analytes were determined by flame atomic absorption spectrometry. After optimization of the complexation and extraction conditions and preconcentration of only 10 ml of sample in the presence of 0.05% Triton X-114, the enhancement factors of 52 and 39 and the detection limits of 0.31 {mu}g l{sup -1} and 1.2 {mu}g l{sup -1} were obtained for cadmium and nickel respectively. The proposed method was applied satisfactorily to the determination of cadmium and nickel in water samples.

  19. Detection of drugs in lifted cyanoacrylate-developed latent fingermarks using two laser desorption/ionisation mass spectrometric methods.

    Science.gov (United States)

    Sundar, Latha; Rowell, Frederick

    2014-02-01

    This paper describes a method for lifting cyanoacrylate (CNA)-developed latent fingermarks from a glass surface and the detection of five drugs in lifted marks from fingers that had been in contact with the drugs, using Surface Assisted Laser Desorption Ionisation Time of Flight Mass Spectrometry (SALDI-TOF-MS) or Matrix Assisted Laser Desorption Ionisation TOF-MS (MALDI-TOF-MS). Two drugs of abuse (cocaine and methadone) and three therapeutic drugs (aspirin, paracetamol and caffeine) were used as contact residues. Latent fingermarks spiked with the drugs were subjected to CNA fuming followed by dusting with ARRO SupraNano™ MS black magnetic powder (SALDI-TOF-MS) or 2,5-dihydroxybenzoic acid (DHB) (MALDI-TOF-MS). The dusted mark was then exposed to solvent vapour before lifting with a commercial fingerprint lifting tape following established procedures. The presence of the drugs was then confirmed by direct analysis on the tape without further processing using SALDI- or MALDI-TOF-MS. The black magnetic fingerprint powder provided visual enhancement of the CNA-fingermark while no visual enhancement was observed for marks dusted with DHB powder. Similar [M + H](+) peaks for all the drug analytes were observed for both methods along with some sodium and potassium adducts for SALDI-MS and some major fragment ions but the SALDI signals were generally more intense. Simple exposure to acetone vapour of the CNA-developed marks enabled their effective transfer onto the tape which was crucial for subsequent MS detection of the analytes.

  20. Rapid assay of rufinamide in dried blood spots by a new liquid chromatography-tandem mass spectrometric method.

    Science.gov (United States)

    la Marca, Giancarlo; Malvagia, Sabrina; Filippi, Luca; Innocenti, Marzia; Rosati, Anna; Falchi, Melania; Pellacani, Simona; Moneti, Gloriano; Guerrini, Renzo

    2011-01-05

    Rufinamide (RUF) is a new antiepileptic drug with efficacy in several types of seizures. The aim of this study was to evaluate the use of dried blood spot (DBS) specimens to determinate RUF levels during treatment. Therapeutic drug monitoring of RUF could be useful in routine clinical practice. Advantages of DBS include short collection time, low invasiveness, ease and low cost of sample collection, transport and storage. The analysis was performed in selected reaction monitoring (SRM) mode. The calibration curve in matrix was linear in the concentration range of 0.008-0.8 mg/L (0.48-47.60 mg/L in DBS) of rufinamide with correlation coefficient value of 0.996. In the concentration range of 0.48-47.6 mg/L, the coefficients of variation in DBS were in the range 1.58-4.67% and the accuracy ranged from 89.73% to 107.32%. The sensitivity and specificity of tandem mass spectrometry allow now high throughput rufinamide analysis. This new assay has favourable characteristics being highly precise and accurate. The published HPLC-UV methods also proved to be precise and accurate, but required not less than 0.2-0.5 mL of plasma and are therefore unsuitable for sample collection in neonates in whom obtaining larger blood samples is not convenient or possible.

  1. Comparison of two feature selection methods for the separability analysis of intertidal sediments with spectrometric datasets in the German Wadden Sea

    Science.gov (United States)

    Jung, Richard; Ehlers, Manfred

    2016-10-01

    The spectral features of intertidal sediments are all influenced by the same biophysical properties, such as water, salinity, grain size or vegetation and therefore they are hard to separate by using only multispectral sensors. This could be shown by a previous study of Jung et al. (2015). A more detailed analysis of their characteristic spectral feature has to be carried out to understand the differences and similarities. Spectrometry data (i.e., hyperspectral sensors), for instance, have the opportunity to measure the reflection of the landscape as a continuous spectral pattern for each pixel of an image built from dozen to hundreds of narrow spectral bands. This reveals a high potential to measure unique spectral responses of different ecological conditions (Hennig et al., 2007). In this context, this study uses spectrometric datasets to distinguish between 14 different sediment classes obtained from a study area in the German Wadden Sea. A new feature selection method is proposed (Jeffries-Matusita distance bases feature selection; JMDFS), which uses the Euclidean distance to eliminate the wavelengths with the most similar reflectance values in an iterative process. Subsequent to each iteration, the separation capability is estimated by the Jeffries-Matusita distance (JMD). Two classes can be separated if the JMD is greater than 1.9 and if less than four wavelengths remain, no separation can be assumed. The results of the JMDFS are compared with a state-of-the-art feature selection method called ReliefF. Both methods showed the ability to improve the separation by achieving overall accuracies greater than 82%. The accuracies are 4%-13% better than the results with all wavelengths applied. The number of remaining wavelengths is very diverse and ranges from 14 to 213 of 703. The advantage of JMDFS compared with ReliefF is clearly the processing time. ReliefF needs 30 min for one temporary result. It is necessary to repeat the process several times and to average

  2. [Oil atomic spectrometric feature selection by Parzen window based vague sets theory].

    Science.gov (United States)

    Xu, Chao; Zhang, Pei-Lin; Ren, Guo-Quan; Zhang, Xiao-Dong; Yang, Yu-Dong

    2011-02-01

    Large quantity and ambiguity of oil atomic spectrometric information greatly affects the applicable efficiency and accuracy in fault diagnosis. A novel method for choosing less and effective spectrometric features is presented. Based on gearbox test bed, we simulated the normal wear state and two typical faults to acquire the lubricant samples. The three wear states are regarded as three vague sets, and spectrometric feature values are vague values on vague sets. Based on similarity between vague values, mean vague sensibility (MVS) is defined to describe the sensitive degree of spectrometric feature to wear state. Besides, the membership degrees of vague sets greatly depend on human experience. The probability density distribution of spectrometric data of three wear states was estimated with Parzen window. Combined with Bayesian formula, the range of vague sets membership was calculated. Experimental results verify that the proposed method is of efficient help in choosing high fault-sensitive features from so many spectrometric features.

  3. Determination of antimycin-A in water by liquid chromatographic/mass spectrometry: single-laboratory validation.

    Science.gov (United States)

    Bernardy, Jeffry A; Hubert, Terrance D; Ogorek, Jacob M; Schmidt, Larry J

    2013-01-01

    An LC/MS method was developed and validated for the quantitative determination and confirmation of antimycin-A (ANT-A) in water from lakes or streams. Three different water sample volumes (25, 50, and 250 mL) were evaluated. ANT-A was stabilized in the field by immediately extracting it from water into anhydrous acetone using SPE. The stabilized concentrated samples were then transported to a laboratory and analyzed by LC/MS using negative electrospray ionization. The method was determined to have adequate accuracy (78 to 113% recovery), precision (0.77 to 7.5% RSD with samples > or = 500 ng/L and 4.8 to 17% RSD with samples < or = 100 ng/L), linearity, and robustness over an LOQ range from 8 to 51 600 ng/L.

  4. Determination of Antimycin-A in water by liquid chromatographic/mass spectrometry: single-laboratory validation

    Science.gov (United States)

    Bernardy, Jeffry A.; Hubert, Terrance D.; Ogorek, Jacob M.; Schmidt, Larry J.

    2013-01-01

    An LC/MS method was developed and validated for the quantitative determination and confirmation of antimycin-A (ANT-A) in water from lakes or streams. Three different water sample volumes (25, 50, and 250 mL) were evaluated. ANT-A was stabilized in the field by immediately extracting it from water into anhydrous acetone using SPE. The stabilized concentrated samples were then transported to a laboratory and analyzed by LC/MS using negative electrospray ionization. The method was determined to have adequate accuracy (78 to 113% recovery), precision (0.77 to 7.5% RSD with samples ≥500 ng/L and 4.8 to 17% RSD with samples ≤100 ng/L), linearity, and robustness over an LOQ range from 8 to 51 600 ng/L.

  5. Determination of hexanal in rice using an automated dynamic headspace sampler coupled to a gas chromatograph-mass spectrometer.

    Science.gov (United States)

    Wang, Yiru; Ha, Jaeho

    2013-01-01

    The aim of this study was to establish a method for the determination of hexanal as a lipid oxidation marker in rice. For the sample preparation, ground rice exhibited better sensitivity and reproducibility for the analysis of hexanal than whole rice. A total flow of purge gas of 300 mL at 20 mL/min of purge was sufficient to obtain the necessary sensitivity for the analysis of hexanal in rice. The total time for sample preparation and analysis for individual samples was approximately 15 min. A low incubation temperature of 30°C was chosen, not only to reduce the effect of water, but also to avoid excess lipid oxidation and loss of hexanal during the analysis. The limits of detection and quantification were 3.7 and 5.1 ng/g, respectively. Good linearity was obtained in the range from 5.1-500.0 ng/g. The recoveries of hexanal in rice were greater than 97.0 and 107.0% at the spiked levels of 5 and 50 ng/g, respectively, with relative standard deviations of 3.3 and 6.1%, respectively.

  6. 液相色谱-质谱联用仪的最佳校准条件的选择%Selection of Optimum Calibration Conditions in Calibrating Liquid Chromatograph-mass Spectrometer

    Institute of Scientific and Technical Information of China (English)

    施江焕

    2013-01-01

    Liquid chromatograph and mass spectrometer was coupled together to the analytical instrument by a certain interface.Based on the working principle and structure of Liquid chromatograph-mass spectrometer,for setting the calibration parameter of the instrument,the technique of selecting optimum calibration conditions in calibrating Liquid chromatograph-mass spectrometer was studied by the analysis of the chromatographic conditions,instrument tuning and mass spectrometry conditions.So it could ensure to calibrate Liquid chromatograph-mass spectrometer accurately and provide some guidance on the calibration for Metrological institutions.%液相色谱-质谱联用仪是将液相色谱仪与质谱仪通过一定的接口耦合到一起的分析仪器.本文从色质谱联用仪的工作原理及结构入手,针对仪器校准时的参数设置,通过分析色谱条件、仪器调谐、质谱条件等因素,介绍了色质联用仪最佳校准条件的选择技巧,有力保证了对液质联用仪进行准确的计量校准,为计量检定机构开展校准工作提供了参考.

  7. Integration of Gas Chromatography Mass Spectrometry Methods for Differentiating Ricin Preparation Methods

    Energy Technology Data Exchange (ETDEWEB)

    Wunschel, David S.; Melville, Angela M.; Ehrhardt, Christopher J.; Colburn, Heather A.; Victry, Kristin D.; Antolick, Kathryn C.; Wahl, Jon H.; Wahl, Karen L.

    2012-05-17

    The investigation of crimes involving chemical or biological agents is infrequent, but presents unique analytical challenges. The protein toxin ricin is encountered more frequently than other agents and is found in the seeds of the castor plant Ricinus communis. Typically, the toxin is extracted from castor seeds utilizing a variety of different recipes that result in varying purity of the toxin. Moreover, these various purification steps can also leave or differentially remove a variety of exogenous and endogenous residual components with the toxin that may indicate the type and number of purification steps involved. We have applied three gas chromatographic - mass spectrometric (GC-MS) based analytical methods to measure the variation in seed carbohydrates and castor oil ricinoleic acid as well as the presence of solvents used for purification. These methods were applied to the same samples prepared using four previously identified toxin preparation methods starting from four varieties of castor seeds. The individual data sets for seed carbohydrate profiles, ricinoleic acid or acetone amount each provided information capable of differentiating different types of toxin preparations across seed types. However, the integration of the data sets using multivariate factor analysis provided a clear distinction of all samples based on the preparation method and independent of the seed source. In particular the abundance of mannose, arabinose, fucose, ricinoleic acid and acetone were shown to be important differentiating factors. These complementary tools provide a more confident determination of the method of toxin preparation.

  8. Determination of Palladium in Resin by Lead Fire Assaying-Flame Atomic Absorption Spectrometric Method%铅试金富集-火焰原子吸收光谱法测定树脂中钯

    Institute of Scientific and Technical Information of China (English)

    王芳; 陈小兰; 林海山; 李小玲; 肖红新

    2013-01-01

    通过铅试金富集树脂中的钯并用银作钯灰吹保护,得到的银钯合粒用王水溶解,在5%的盐酸介质中,采用原子吸收光谱法测定钯,该法测钯的相对标准偏差RSD为0.53%,加标回收率在99.04%~100.10%之间。%Palladium in resin was enriched by lead assaying, using silver as a protective agent to produce silver-palladium alloy, and then the alloy was dissolved in aqua regia. Air acetylene flame atomic absorption spectrometric method was used to determinate palladium in 5%hydrochloric acid solution. The relative standard deviation (RSD) in determination of palladium is 0.53%and the recovery rate is between 99.04%~100.10%.

  9. In-house validation of a method for determination of silver nanoparticles in chicken meat based on asymmetric flow field-flow fractionation and inductively coupled plasma mass spectrometric detection

    DEFF Research Database (Denmark)

    Löschner, Katrin; Navratilova, Jana; Grombe, Ringo;

    2015-01-01

    spectrometric detection (AF4-ICP-MS) was applied for quantitative analysis of silver nanoparticles (AgNPs) in a chicken meat matrix following enzymatic sample preparation. For the first time an analytical validation of nanoparticle detection in a food matrix by AF4-ICP-MS has been carried out and the results......Nanomaterials are increasingly used in food production and packaging, and validated methods for detection of nanoparticles (NPs) in foodstuffs need to be developed both for regulatory purposes and product development. Asymmetric flow field-flow fractionation with inductively coupled plasma mass...... showed repeatable and intermediately reproducible determination of AgNP mass fraction and size. The findings demonstrated the potential of AF4-ICP-MS for quantitative analysis of NPs in complex food matrices for use in food monitoring and control. The accurate determination of AgNP size distribution...

  10. Validation of a liquid chromatographic/tandem mass spectrometric method for the determination of scopolamine butylbromide in human plasma: application of the method to a bioequivalence study.

    Science.gov (United States)

    Manfio, Josélia Larger; Dos Santos, Mauricio Bedim; Favreto, Wagner Alex Jann; Hoffmann, Fabiane Ines; Mertin, Adriana Cristina

    2009-01-01

    A sensitive and specific LC/MS/MS method was developed and validated for the determination of scopolamine butylbromide in human plasma. Scopolamine butylbromide and propanolol (internal standard) were extracted from the plasma by liquid-liquid extraction with dichloromethane as the extraction solvent and separated on a C18 analytical column (50 x 4.6 mm id) maintained at 40 degrees C. The analytes were eluted at a constant flow rate of 0.45 mL/min; the mobile phase consisted of acetonitrile and a buffer of 5 mM ammonium acetate and 0.1% formic acid (60 + 40, v/v). The mass spectrometer, equipped with an electrospray source in the positive ionization mode, was set up in the multiple-reaction monitoring mode to monitor the transitions m/z 360.6 > 102.5 (scopolamine butylbromide) and m/z 259.7 > 115.6 (propanolol). The chromatographic separation was obtained within 2.0 min, and the responses were linear over the concentration range of 0.10-40.00 ng/mL. The mean extraction recoveries of scopolamine butylbromide and propanolol from plasma were 69.00 and 80.76%, respectively. Method validation parameters, such as specificity, linearity, precision, accuracy, and stability, were within the acceptable range. Moreover, when the proposed method was successfully applied to a pharmacokinetic study of healthy human volunteers, the results showed that the two scopolamine butylbromide formulations tested are not bioequivalent in rate and extent of absorption.

  11. Quantitative O-glycomics based on improvement of the one-pot method for nonreductive O-glycan release and simultaneous stable isotope labeling with 1-(d0/d5)phenyl-3-methyl-5-pyrazolone followed by mass spectrometric analysis.

    Science.gov (United States)

    Wang, Chengjian; Zhang, Ping; Jin, Wanjun; Li, Lingmei; Qiang, Shan; Zhang, Ying; Huang, Linjuan; Wang, Zhongfu

    2017-01-06

    Rapid, simple and versatile methods for quantitative analysis of glycoprotein O-glycans are urgently required for current studies on protein O-glycosylation patterns and the search for disease O-glycan biomarkers. Relative quantitation of O-glycans using stable isotope labeling followed by mass spectrometric analysis represents an ideal and promising technique. However, it is hindered by the shortage of reliable nonreductive O-glycan release methods as well as the too large or too small inconstant mass difference between the light and heavy isotope form derivatives of O-glycans, which results in difficulties during the recognition and quantitative analysis of O-glycans by mass spectrometry. Herein we report a facile and versatile O-glycan relative quantification strategy, based on an improved one-pot method that can quantitatively achieve nonreductive release and in situ chromophoric labeling of intact mucin-type O-glycans in one step. In this study, the one-pot method is optimized and applied for quantitative O-glycan release and tagging with either non-deuterated (d0-) or deuterated (d5-) 1-phenyl-3-methyl-5-pyrazolone (PMP). The obtained O-glycan derivatives feature a permanent 10-Da mass difference between the d0- and d5-PMP forms, allowing complete discrimination and comparative quantification of these isotopically labeled O-glycans by mass spectrometric techniques. Moreover, the d0- and d5-PMP derivatives of O-glycans also have a relatively high hydrophobicity as well as a strong UV adsorption, especially suitable for high-resolution separation and high-sensitivity detection by RP-HPLC-UV. We have refined the conditions for the one-pot reaction as well as the corresponding sample purification approach. The good quantitation feasibility, reliability and linearity of this strategy have been verified using bovine fetuin and porcine stomach mucin as model O-glycoproteins. Additionally, we have also successfully applied this method to the quantitative O

  12. Development and validation of a sensitive liquid chromatographic-tandem mass spectrometric method for the simultaneous analysis of granisetron and 7-hydroxy granisetron in human plasma and urine samples: application in a clinical pharmacokinetic study in pregnant subject.

    Science.gov (United States)

    Zhao, Yang; Chen, Hui-Jun; Caritis, Steve; Venkataramanan, Raman

    2016-02-01

    A liquid chromatography-tandem mass spectrometric method for the quantification of granisetron and its major metabolite, 7-hydroxy granisetron in human plasma and urine samples was developed and validated. Respective stable isotopically labeled granisetron and 7-hydroxy granisetron were used as internal standards (IS). Chromatography was performed using an Xselect HSS T3 analytical column with a mobile phase of 20% acetonitrile in water (containing 0.2 mM ammonium formate and 0.14% formic acid, pH 4) delivered in an isocratic mode. Tandem mass spectrometry operating in positive electrospray ionization mode with multiple reaction monitoring was used for quantification. The standard curves were linear in the concentration ranges of 0.5-100 ng/mL for granisetron and 0.1-100 ng/mL for 7-hydroxy granisetron in human plasma samples, and 2-2000 ng/mL for granisetron and 2-1000 ng/mL for 7-hydroxy granisetron in human urine samples, respectively. The accuracies were >85% and the precision as determined by the coefficient of variations was validated method was successfully applied to a pharmacokinetic study after intravenous administration of 1 mg granisetron to a pregnant subject.

  13. Determination of aminopolycarboxylic acids in river water by solid-phase extraction on activated charcoal cartridges and gas chromatography with mass spectrometric detection. Method performance characteristics and estimation of the uncertainty.

    Science.gov (United States)

    Jiménez, Juan J

    2013-04-03

    A new sample preparation procedure to determine aminopolycarboxylic acids (ethylenediaminetetraacetic acid, EDTA, nitrilotriacetic acid, NTA, diethylenetriaminepentaacetic acid, DTPA, and cyclohexanediaminetetraacetic acid, CDTA) in river water is described. The procedure consists of the solid-phase extraction of the aminopolycaroxyllic acids on activated charcoal cartridges after increasing the ionic strength and acidifying the sample. The extract was eluted with methanol and the analytes were methylated in presence of BF3/methanol to determine them by GC with mass spectrometric detection. Recoveries were higher than 90% with good repeatabilities and inter-day precision for concentrations close to quantification limits (about 10 μg L(-1)) and higher. It has been verified that the proposed method is robust according to the Youden and Steiner test and free of matrix effects arisen from the presence of organic matter and iron(III) as deduced from statistical tests. A bottom-up approach was followed to estimate the uncertainty of the measured concentration. At concentrations close to 10 μg L(-1) the most relevant step of the method is the calculus of the interpolated concentration which has a high value of relative standard uncertainty.

  14. Determination of organic chemicals in human whole blood: Preliminary method development for volatile organics

    Energy Technology Data Exchange (ETDEWEB)

    Cramer, P.H.; Boggess, K.E.; Hosenfeld, J.M. (Midwest Research Institute, Kansas City, MO (USA)); Remmers, J.C.; Breen, J.J.; Robinson, P.E.; Stroup, C. (Environmental Protection Agency, Washington, DC (USA))

    1988-05-01

    Extensive commercial, industrial, and domestic use of volatile organic chemicals, virtually assures that the general population will be exposed to some level of this class of chemicals. Because blood interacts with the respiratory system and is a major component of the body, it is likely that the analysis of blood will show exposure to volatile organics. Monitoring of the blood in conjunction with monitoring of xenobiotic levels in urine and adipose tissue is an effective way to assess the total body burden resulting from exposure to a chemical. This article introduces a method for the detection and confirmation of selected volatile organics at parts-per-trillion (ppt) levels in whole human blood. Intended for routine use, the method consists of a dynamic headspace purge of water-diluted blood where a carrier gas sweeps the surface of the sample and removes a quantifiable amount of the volatile organics from the blood and into an adsorbent trap. The organics are thermally desorbed from the adsorbent trap and onto the analytical column in a gas-chromatographic/mass-spectrometric (GC/MS) system where limited mass-scan data are taken for qualitative and quantitative identification. Method validation results and limited population-survey results are also presented here.

  15. 气相色谱质谱联用仪一机多用的改进%Simultaneousl application of dual-column and dual detectors on chromatograph-mass spectrometry-FID system

    Institute of Scientific and Technical Information of China (English)

    朱建设

    2014-01-01

    应用双进样口、双毛细管色谱柱以及质谱检测器(M SD )和氢火焰检测器(FID ),通过四通分流装置在一台带FID的气相色谱质谱联用仪(GCMS)上面实现一根毛细管柱同时采集MSD和FID双检测器信号数据;同时安装两根不同极性的柱子,不需要拆装柱子,进行无痕切换使用来满足不同样品分析要求。%This paper introduces the mathod of MSD and FID simultaneous detection in 6890N/5975C gas chromatograph-mass spectrometer and the mathod can meet different analysis without column ex-change .

  16. Development, validation and application of an ultra high performance liquid chromatographic-tandem mass spectrometric method for the simultaneous detection and quantification of five different classes of veterinary antibiotics in swine manure.

    Science.gov (United States)

    Van den Meersche, Tina; Van Pamel, Els; Van Poucke, Christof; Herman, Lieve; Heyndrickx, Marc; Rasschaert, Geertrui; Daeseleire, Els

    2016-01-15

    In this study, a fast, simple and selective ultra high performance liquid chromatographic-tandem mass spectrometric (UHPLC-MS/MS) method for the simultaneous detection and quantification of colistin, sulfadiazine, trimethoprim, doxycycline, oxytetracycline and ceftiofur and for the detection of tylosin A in swine manure was developed and validated. First, a simple extraction procedure with acetonitrile and 6% trichloroacetic acid was carried out. Second, the supernatant was evaporated and the pellet was reconstituted in 1 ml of water/acetonitrile (80/20) and 0.1% formic acid. Extracts were filtered and analyzed by UHPLC-MS/MS on a Kinetex C18 column using gradient elution. The method developed was validated according to the criteria of Commission Decision 2002/657/EC. Recovery percentages varied between 94% and 106%, repeatability percentages were within the range of 1.7-9.2% and the intralaboratory reproducibility varied between 2.8% and 9.3% for all compounds, except for tylosin A for which more variation was observed resulting in a higher measurement uncertainty. The limit of detection and limit of quantification varied between 1.1 and 20.2 and between 3.5 and 67.3 μg/kg, respectively. This method was used to determine the presence and concentration of the seven antibiotic residues in swine manure sampled from ten different manure pits on farms where the selected antibiotics were used. A link was found between the antibiotics used and detected, except for ceftiofur which is injected at low doses and degraded readily in swine manure and was therefore not recovered in any of the samples. To the best of our knowledge, this is the first method available for the simultaneous extraction and quantification of colistin with other antibiotic classes. Additionally, colistin was never extracted from swine manure before. Another innovative aspect of this method is the simultaneous detection and quantification of five different classes of antibiotic residues in swine manure.

  17. A Validated High-Performance Liquid Chromatography-Tandem Mass Spectrometric (Lc-Ms/Ms Method for Simultaneous Determination of R(+-Ketorolac and S(−-Ketorolac in Human Plasma and Its Application to a Bioequivalence Study

    Directory of Open Access Journals (Sweden)

    Sabyasachi Patri

    2011-01-01

    Full Text Available We report a selective, accurate, and reproducible liquid chromatography-tandem mass spectrometric (LC-MS/MS method that employs solid phase extraction for quantification of ketorolac enantiomers in human plasma. Resolution of R(+-ketorolac and S(−-ketorolac was achieved using a Chiral-AGP column and a mobile phase of ammonium formate buffer (10 mM, pH 4.70±0.05:acetonitrile (85 : 15, v/v and 70 : 30, v/v in a gradient time program. S(+-etodolac was used as the internal standard (IS. Quantification was achieved using a positive electrospray ionization (ESI+ interface under multiple reaction monitoring (MRM condition. The method was validated over the concentration range of 9.36–1198.69 ng/ml for R(+-ketorolac and 6.07–776.74 ng/ml for S(−-ketorolac. Matrix effect was found negligible and the method showed good performances in terms of accuracy (89.6–102.7% and precision (1.7–6.7% for both enantiomers. Extraction recoveries of R(+-ketorolac, S(−-ketorolac, and S(+-etodolac were 82.04, 70.94, and 93.90%, respectively. Results of all stability exercises in human plasma were within acceptable limits. The method was successfully applied to a single dose cross over bioequivalence study in healthy human male volunteers. Incurred Sample Reanalysis (ISR was performed by randomly selecting 10% of total subject samples of the study using Statistical Analysis Software (SAS. Values of 91.1% for R (+-ketorolac and 83.5% for S(−-ketorolac indicated good acceptance for ISR.

  18. Determinação espectrométrica dos flavonóides das folhas de Maytenus (Celastraceae e de Passiflora (Passifloraceae e comparação com método CLAE-UV Spectrometric determination of flavonoids from Maytenus (Celastraceae and Passiflora (Passifloraceae leaves and comparison with an HPLC-UV method

    Directory of Open Access Journals (Sweden)

    Regina de A. O. Chabariberi

    2009-12-01

    Full Text Available Este trabalho apresenta uma modificação dos procedimentos descritos nas Farmacopéias Francesa e Européia para a análise de flavonoides de Passiflora incarnata L., Passifloraceae, por espectrometria UV-Visível e propõe a sua aplicação na determinação dos flavonoides totais das folhas da espinheira-santa (Maytenus aquifolium Mart. e Maytenus ilicifolia (Schrad. Planch., Celastraceae e do maracujá (Passiflora edulis Sims. e Passiflora alata Curtis, Passifloraceae. Os resultados obtidos por espectrometria no UV-Visível foram comparados aos obtidos por cromatografia líquida de alta eficiência (CLAE-UV, encontrando-se resultados estatisticamente similares entre os métodos espectrométrico modificado da Farmacopéia Francesa e CLAE-UV.This paper reports on a modification of the spectrometric procedures originally described in the French and European Pharmacopoeia for the analysis of Passiflora incarnata L. (Passifloraceae flavonoids, proposing its application in the determination of total flavonoids from "espinheira-santa" (Maytenus aquifolium Mart. and Maytenus ilicifolia (Schrad. Planch., Celastraceae and "maracujá" leaves (Passiflora edulis Sims and Passiflora alata Curtis, Passifloraceae. A comparison was made of the results obtained by the spectrometric procedure with those obtained by high performance liquid chromatography (HPLC-UV, which demonstrated complete compatibility between the modified French Pharmacopoeia (spectrometric and HPLC-UV methods.

  19. A sensitive gas chromatographic-tandem mass spectrometric method for detection of alkylating agents in water: application to acrylamide in drinking water, coffee and snuff.

    Science.gov (United States)

    Pérez, Hermes Licea; Osterman-Golkar, Siv

    2003-08-01

    A sensitive analytical method for the analysis of acrylamide and other electrophilic agents in water has been developed. The amino acid L-valine served as a nucleophilic trapping agent. The method was applied to the analysis of acrylamide in 0.2-1 mL samples of drinking water or Millipore-filtered water, brewed coffee, or water extracts of snuff. The reaction product, N-(2-carbamoylethyl)valine, was incubated with pentafluorophenyl isothiocyanate to give a pentafluorophenylthiohydantoin (PFPTH) derivative. This derivative was extracted with diethyl ether, separated from excess reagent and impurities by a simple extraction procedure, and analyzed by gas chromatography-tandem mass spectrometry. (2H3)Acrylamide, added before the reaction with L-valine, was used as internal standard. Acrylamide and the related compound, N-methylolacrylamide, gave the same PFPTH derivative. The concentrations of acrylamides were acrylamide L(-1)) in water, 200 to 350 nmol L(-1) in brewed coffee, and 10 to 34 nmol g(-1) snuff in portion bags, respectively. The precision (the coefficient of variation was 5%) and accuracy of the method were good. The detection limit was considerably lower than that of previously published methods for the analysis of acrylamide.

  20. An ultra performance liquid chromatography-time-of-flight-mass spectrometric method for fast analysis of ginsenosides in Panax ginseng root

    NARCIS (Netherlands)

    Hu, C.; Kong, H.; Zhu, C.; Wei, H.; Hankemeier, T.; Greef, J. van der; Wang, M.; Xu, G.

    2011-01-01

    A method for fast analysis of ginsenosides in Panax ginseng roots was developed using ultra performance liquid chromatography-time-of-flight-mass spectrometry (UPLC-TOF-MS). The column used was HSS T3 (100 mm × 2.1 mm, 1.8 µm). The mobile phase consisted of 15 mmol/L ammonium formate and acetonitril

  1. Quantitative determination of several toxicological important mycotoxins in pig plasma using multi-mycotoxin and analyte-specific high performance liquid chromatography-tandem mass spectrometric methods.

    Science.gov (United States)

    Devreese, Mathias; De Baere, Siegrid; De Backer, Patrick; Croubels, Siska

    2012-09-28

    A sensitive and reliable multi-mycotoxin method was developed for the identification and quantification of several toxicological important mycotoxins such as deoxynivalenol (DON), deepoxy-deoxynivalenol (DOM-1), T-2 toxin (T-2), HT-2 toxin (HT-2), zearalenone (ZON), zearalanone (ZAN), α-zearalenol (α-ZOL), β-zearalenol (β-ZOL), α-zearalanol (α-ZAL), β-zearalanol (β-ZAL), ochratoxin A (OTA), fumonisin B1 (FB1) and aflatoxin B1 (AFB1) in pig plasma using liquid chromatography combined with heated electrospray ionization triple quadrupole tandem mass spectrometry (LC-h-ESI-MS/MS). Sample clean-up consisted of a deproteinization step using acetonitrile, followed by evaporation of the supernatant and resuspension of the dry residue in water/methanol (85/15, v/v). Each plasma sample was analyzed twice, i.e. once in the ESI+ and ESI- mode, respectively. This method can be used for the assessment of animal exposure to mycotoxins and in the diagnosis of mycotoxicoses. For the performance of toxicokinetic studies with individual mycotoxins, highly sensitive analyte-specific LC-MS/MS methods were developed. The multi-mycotoxin and analyte-specific methods were in-house validated: matrix-matched calibration graphs were prepared for all compounds and correlation and goodness-of-fit coefficients ranged between 0.9974-0.9999 and 2.4-15.5%, respectively. The within- and between-run precision and accuracy were evaluated and the results fell within the ranges specified. The limits of quantification for the multi-mycotoxin and analyte-specific methods ranged from 2 to 10 ng/mL and 0.5 to 5 ng/mL, respectively, whereas limits of detection fell between 0.01-0.52 ng/mL and <0.01-0.15 ng/mL, respectively.

  2. Optimization and validation of a quantitative liquid chromatography-tandem mass spectrometric method covering 295 bacterial and fungal metabolites including all regulated mycotoxins in four model food matrices.

    Science.gov (United States)

    Malachová, Alexandra; Sulyok, Michael; Beltrán, Eduardo; Berthiller, Franz; Krska, Rudolf

    2014-10-01

    An LC-MS/MS "dilute and shoot" method for the determination of 295 fungal and bacterial metabolites was optimized and validated according to the guidelines established in the Directorate General for Health and Consumer Affairs of the European Commission (SANCO) document No. 12495/2011. Four different types of food matrices were chosen for validation: apple puree for infants (high water content), hazelnuts (high fat content), maize (high starch and low fat content) and green pepper (difficult or unique matrix). Method accuracy and precision was evaluated using spiked samples in five replicates at two concentration levels. Method trueness was demonstrated through participation in various proficiency tests. Although the method covers a total number of 331 analytes, validation data were acquired only for 295 analytes, either due to the non-availability of analytical standards or due other reasons described in this paper. Concerning the apparent recovery, the percentage of 295 analytes matching the acceptable recovery range of 70-120% lied down by SANCO varied from 21% in green pepper to 74% in apple puree at the highest spiking level. At the levels close to limit of quantification only 20-58% of the analytes fulfilled this criterion. The extent of matrix effects was strongly dependent on the analyte/matrix combination. In general, the lowest matrix effects were observed in apple puree (59% of analytes were not influenced by enhancement/suppression at all at the highest validation level). The highest matrix effects were observed in green pepper, where only 10% of analytes did not suffer from signal suppression/enhancement. The repeatability of the method was acceptable (RSD≤20) for 97% of all analytes in apple puree and hazelnuts, for 95% in maize and for 89% in green pepper. Concerning the trueness of the method, Z-scores were generally between -2 and 2, despite a broad variety of different matrices. Based on these results it can be concluded that quantitative

  3. [Butanol extraction combined with dilute hydrochloric acid dissolution-atomic fluorescence spectrometric method for indirect determination of molybdenum in Chinese herbal medicine].

    Science.gov (United States)

    Lu, Jian-Ping; Geng, Guo-Xing; Tang, Yan-Kui; Lu, Zhi-Yong

    2012-12-01

    A method for indirectly determining the molybdenum in Chinese herbal medicine by butanol extraction and dilute hydrochloric acid dissolution was established for atomic fluorescence spectrometry. The molybdoarsenate heteropoly acid, formed in the presence of As(V) and ammonium molybdate in 0.3 mol x L(-1) sulphuric acid medium, was separated and enriched in the organic solvent, then the evaporation of organic reagent was implemented and the left residue was dissolved in dilute hydrochloric acid in which the arsenic content was determined on behalf of molybdenum. In the optimum experimental conditions, molybdenum content in 0-15 microg x L(-1) range depicts a good linear relationship, the detection limit and relative standard deviation of 0.44 microg x L(-1) and 1.1% were obtained, respectively. Spiked Chinese herbal medicine samples were determined with the proposed method, and recoveries of 95.6%-101.3% were achieved.

  4. Direct and efficient liquid chromatographic-tandem mass spectrometric method for opiates in urine drug testing - importance of 6-acetylmorphine and reduction of analytes.

    Science.gov (United States)

    Andersson, Maria; Stephanson, Nikolai; Ohman, Inger; Terzuoli, Tommy; Lindh, Jonatan D; Beck, Olof

    2014-04-01

    Opiates comprise a class of abused drugs that is of primary interest in clinical and forensic urine drug testing. Determination of heroin, codeine, or a multi-drug ingestion is complicated since both heroin and codeine can lead to urinary excretion of free and conjugated morphine. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) offers advantage over gas chromatography-mass spectrometry by simplifying sample preparation but increases the number of analytes. A method based on direct injection of five-fold diluted urine for confirmation of morphine, morphine-3-glucuronide, morphine-6-glucuronide, codeine, codeine-6-glucuronide and 6-acetylmorphine was validated using LC-MS/MS in positive electrospray mode monitoring two transitions using selected reaction monitoring. The method was applied for the analysis of 3155 unknown urine samples which were positive for opiates in immunochemical screening. A linear response was observed for all compounds in the calibration curves covering more than three orders of magnitude. Cut off was set to 2 ng/ml for 6-acetylmorphine and 150 ng/ml for the other analytes. 6-Acetylmorphine was found to be effective (sensitivity 82%) in detecting samples as heroin intake. Morphine-3-glucuronide and codeine-6-glucuronide was the predominant components of total morphine and codeine, 84% and 93%, respectively. The authors have validated a robust LC-MS/MS method for rapid qualitative and quantitative analysis of opiates in urine. 6-Acetylmorphine has been demonstrated as a sensitive and important parameter for a heroin intake. A possible interpretation strategy to conclude the source of detected analytes was proposed. The method might be further developed by reducing the number of analytes to morphine-3-glucuronide, codeine-6-glucuronide and 6-acetylmorphine without compromising test performance.

  5. A liquid chromatography-atmospheric pressure photoionization tandem mass spectrometric (LC-APPI-MS/MS) method for the determination of triterpenoids in medicinal plant extracts.

    Science.gov (United States)

    Gobo, Luciana Assis; Viana, Carine; Lameira, Osmar Alves; de Carvalho, Leandro Machado

    2016-08-01

    An analytical method using liquid chromatography-atmospheric pressure photoionization tandem mass spectrometry with toluene as a dopant was developed for the determination of triterpenes in medicinal plant extracts. The 12 compounds determined have been shown to exhibit biological activity, such as gastroprotective, hepatoprotective, anti-inflammatory, antiviral and anti-tumor effects. The parameters of the atmospheric pressure photoionization interface were optimized to obtain the highest possible sensitivity for all of the compounds. The limits of detection and quantification ranged from 0.4 to 157.9 µg l(-1) and 1.3 to 526.4 µg l(-1) , respectively. The method was validated and applied to extracts of five medicinal plants species (Mansoa alliacea (Lam.) A.H.Gentry, Bauhinia variegata var variegata, Bauhinia variegata var alboflava, Cecropia obtuse Trécul and Cecropia palmate Willd) from the Amazonian region. The concentrations of the six triterpenes quantified in the samples ranged from 0.424 mg kg(-1) for ursolic acid to 371.96 mg kg(-1) for β-amyrin, which were quantified by using the standard addition method (n = 3). Copyright © 2016 John Wiley & Sons, Ltd.

  6. Development and validation of a liquid chromatographic/ tandem mass spectrometric method for determination of chlortetracycline, oxytetracycline, tetracycline, and doxycycline in animal feeds.

    Science.gov (United States)

    Guo, Liang; Chen, Yiqiang; Zhang, Liying; Yang, Wenjun; He, Pingli

    2012-01-01

    A selective and accurate LC/MS/MS method for the simultaneous determination of chlortetracycline (CTC), oxytetracycline (OTC), tetracycline (TC), and doxycycline (DC) in animal feeds was developed. Samples were extracted with Na2EDTA-McIlvaine buffer and further purified with Oasis HLB SPE columns. The purified extract was separated on an Xbridge C18 column and detected by LC/MS/MS with positive electrospray ionization in the multiple reaction monitoring mode. This method provided average recoveries of 80.9 to 119.5%, with CVs of 1.7 to 9.8% in the range of 0.5 to 50 mg/kg CTC, OTC, TC, and DC in feeds, except the average recovery of CTC was 76.0%, with a CV of 14.6% in pig feed spiked with 0.5 mg/kg CTC. The linear ranges for the four TCs determined by LC/MS/MS ranged from 0.005 to 2.5 microg/mL with a linear correlation coefficient (R2) >0.99. The LOD and LOQ for CTC, OTC, TC, and DC in pig and poultry feeds ranged from 0.003 to 0.02 and 0.01 to 0.05 microg/g, respectively. The method was successfully applied for the analysis of 30 real feed samples, and no illegal use was detected.

  7. Validation of a fully automated high throughput liquid chromatographic/tandem mass spectrometric method for roxithromycin quantification in human plasma. Application to a bioequivalence study.

    Science.gov (United States)

    Kousoulos, Constantinos; Tsatsou, Georgia; Dotsikas, Yannis; Apostolou, Constantinos; Loukas, Yannis L

    2008-05-01

    A fully automated high-throughput liquid chromatography/tandem mass spectrometry (LC-MS/MS) method was developed for the determination of roxithromycin in human plasma. The plasma samples were treated by liquid-liquid extraction (LLE) in 2.2 mL 96-deep-well plates. Roxithromycin and the internal standard clarithromycin were extracted from 100 microL of human plasma by LLE, using methyl t-butyl ether as the organic solvent. All liquid transfer steps were performed automatically using robotic liquid handling workstations. After vortexing, centrifugation and freezing, the supernatant organic solvent was evaporated and reconstituted. Sample analysis was performed by reversed-phase LC-MS/MS, with positive ion electrospray ionization, using multiple-reaction monitoring. The method had a very short chromatographic run time of 1.6 min. The calibration curve was linear for the range of concentrations 50.0-20.0x10(3) ng mL(-1). The proposed method was fully validated and it was proven to be selective, accurate, precise, reproducible and suitable for the determination of roxithromycin in human plasma. Therefore, it was applied to the rapid and reliable determination of roxithromycin in a bioequivalence study after per os administration of 300 mg tablet formulations of roxithromycin.

  8. An Ultra-High Performance Liquid Chromatographic-Tandem Mass Spectrometric Method for the Determination of Sinomenine in Human Plasma after Transdermal Delivery of the Zhengqing Fengtongning Injection

    Directory of Open Access Journals (Sweden)

    Tingbo Chen

    2015-04-01

    Full Text Available A sensitive, precise and selective ultra-high performance liquid chromatography method coupled with triple-quadrupole mass spectrometry was developed and validated for the determination of trace amounts of sinomenine (ng/mL in minute volumes of human plasma. Fifty microliter plasma samples were precipitated using methanol to extract sinomenine. Separation was carried out on a C18 column with a water and acetonitrile mobile phase gradient with formic acid as an additive. The mass spectrometry data were obtained in the positive ion mode, and the transition of multiple reactions was monitored at m/z 330.2→181.0 for sinomenine quantification. The working assay range for sinomenine was linear from 0.1173 to 15.02 ng/mL with the lower limit of quantification of 0.1173 ng/mL. The precision and accuracy of the method was less than 15% in intra-day and inter-day experiments with a matrix effect of less than 6.5%. After validation, the quantitative method was applied to analyze sinomenine levels in human plasma after transdermal delivery of the Zhengqing Fengtongning Injection. The results showed that some samples contained sinomenine within the concentration range 0.4131–4.407 ng/mL.

  9. Validation of a novel, fully automated high throughput high-performance liquid chromatographic/tandem mass Spectrometric method for quantification of pantoprazole in human plasma.

    Science.gov (United States)

    Dotsikas, Yannis; Apostolou, Constantinos; Soumelas, Stefanos; Kolocouri, Filomila; Ziaka, Afroditi; Kousoulos, Constantinos; Loukas, Yannis L

    2010-01-01

    An automated high-throughput HPLC/MS/MS method was developed for the quantitative determination of pantoprazole in human plasma. Only 100 microL plasma was placed in 2.2 mL 96 deep-well plates, and both pantoprazole and omeprazole (IS) were extracted from human plasma by liquid-liquid extraction, using diethyl ether-dichloromethane (70:30, v/v) as the organic solvent. Robotic liquid-handling workstations were used for all liquid transfer and solution preparation steps and resulted in a short sample preparation time. After vortexing, centrifugation, and freezing, the supernatant organic solvent was evaporated and reconstituted in a small volume of reconstitution solution. Sample analysis was performed by utilizing the combination of RP-HPLC/MS/MS, with positive-ion electrospray ionization and multiple reaction monitoring detection. The chromatographic run time was set at 1.8 min with a flow rate of 0.6 mL/min on a Nucleosil octylsilyl (C8) analytical column. The method was proven to be sensitive, specific, accurate, and precise for the determination of pantoprazole in human plasma. The method was applied to a bioequivalence study after per os administration of a 40 mg pantoprazole gastric retentive tablet.

  10. Advanced ultra-performance liquid chromatography-photodiode array-quadrupole time-of-flight mass spectrometric methods for simultaneous screening and quantification of triterpenoids in Poria cocos.

    Science.gov (United States)

    Xia, Bing; Zhou, Yan; Tan, Hong Sheng; Ding, Li Sheng; Xu, Hong Xi

    2014-01-01

    A sensitive, precise and accurate method was developed to screen and quantify triterpenoids based on ultra-performance liquid chromatography-photodiode array-quadrupole time-of-flight mass spectrometry (UPLC-PDA-QTOF-MS). An exact neutral loss scan of 62.0004 Da (CH2O3) was used to selectively detect triterpenoids in Poria cocos, followed by a survey scan for exact masses of precursor and fragment ions of these triterpenoids. The developed method was applied to quantify seven major triterpenoids in 40 P. cocos samples of different origins within 18 min, and a total of 31 triterpenoids were unequivocally or tentatively identified. Principal component analysis of these samples showed a clear separation of three groups, and ten triterpenoids play key roles in differentiating these samples were obtained from the OPLS-DA variable influence on projection (VIP) plot and then unequivocally or tentatively identified. The developed method can be applied for rapid bitterness evaluation, quality control and authenticity establishment of P. cocos.

  11. Development of an isotope labeling ultra-high performance liquid chromatography mass spectrometric method for quantification of acylglycines in human urine

    Energy Technology Data Exchange (ETDEWEB)

    Stanislaus, Avalyn; Guo, Kevin [Department of Chemistry, University of Alberta, Edmonton, Alberta (Canada); Li Liang, E-mail: Liang.Li@ualberta.ca [Department of Chemistry, University of Alberta, Edmonton, Alberta (Canada)

    2012-10-31

    Graphical abstract: - Abstract: Acylglycines play a crucial regulatory and detoxification role in the accumulation of the corresponding acyl CoA esters and are an important class of metabolites in the diagnoses of inborn errors of metabolism. Sensitive quantification of a large number of acylglycines not only improves diagnosis but also enables the discovery of potential new biomarkers of diseases. We report an ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS) method for quantifying acylglycines in human urine with high sensitivity. This method is based on the use of a newly developed isotope labeling reagent, p-dimethylaminophenacyl (DmPA) bromide, to label acylglycines to improve detection sensitivity. Eighteen acylglycines, namely acetylglycine, propionylglycine, isobutyrylglycine, butyrylglycine, 4-hydroxyphenylacetylglycine, 2-furoylglycine, tiglylglycine, 2-methybutyrylglycine, 3-methylcrotonylglycine, isovalerylglycine, valerylglycine, hexanoylglycine, phenylacetylglycine, phenylpropionylglycine, glutarylglycine, heptanoylglycine, octanoylglycine and suberylglycine, were measured. This method uses calibration standards prepared in surrogate matrix (un-derivatized urine) and stable-isotope labeled analytes as the internal standards. The analysis was carried out in the positive ion detection mode using multiple reaction monitoring (MRM) survey scans. The calibration curves were validated over the range of 1.0-500 nM. The method achieved a lower limit of quantitation (LLOQ) of 1-5 nM for all analytes, as measured by the standard derivations associated with calibration curves and confirmed in surrogate matrix; the signal-to-noise ratio at LLOQ ranged from 12.50 to 156.70. Both accuracy (% RE or relative error) and precision (% CV) were <15%. Matrix effects were minimized using the surrogate matrix. All eighteen analytes were stable in urine for at least 5 h at room temperature, autosampler (4 Degree-Sign C) for 24 h, 7 weeks at -20

  12. Gas chromatographic–mass spectrometric validated method for the determination of Bisphenol A in public-supply water: An investigation in Campo Grande, MS, Brazil

    Directory of Open Access Journals (Sweden)

    Émerson Montagner

    2013-01-01

    Full Text Available A new validated method is described for determining bisphenol A (BPA in surface and public-supply water samples. Recovery rates of 91% to 113%, with coefficients of variation below 8.9%, were obtained within the limit of detection (2.4 ng L–1. Concentrations of 13 to 113 ng L–1 were found in tap water. An analysis of BPA stability in solid-phase extraction cartridges revealed that the analyte can be stored in such containers for at least 90 days. An evaluation of BPA leached from polyvinyl chloride (PVC piping showed that BPA can contaminate water distribution systems.

  13. Liquid chromatography-mass spectrometric method for determination of the non-imidazole H3-receptor antagonist UPR1056 in rat plasma.

    Science.gov (United States)

    Vacondio, Federica; Silva, Claudia; Morini, Giovanni; Bordi, Fabrizio; Flammini, Lisa; Barocelli, Elisabetta; Mor, Marco

    2011-07-01

    The non-imidazole H3 receptor antagonist UPR1056 was dosed in plasma samples from rats individually administered with a single i.p. dose of 1.25 mg/kg by means of a newly validated HPLC-MS method. UPR1056 was extracted from rat plasma by protein precipitation with acetonitrile and was separated by linear gradient elution, employing water and methanol both additioned with 0.05% trifluoroacetic acid as mobile phases. UPR1056 was detected in MS using an electrospray ion source operating in positive ion mode. Acquisition was performed in single ion monitoring mode at m/z=349.3. The method was validated over the concentration range of 17.43-1743 ng/mL (50-5000 pmol/mL). Within- and between-run precision for the low, mid and high quality controls (QC) levels were 6.75% or less and accuracy ranged from 95.8 to 107.6%. The lower limit of quantification was 17.43 ng/mL. The analysis of the time course of UPR1056 concentrations over the 24-h period revealed a C(max) of 1147 ng/mL after 2 h from peripheral administration of the non-imidazole H(3)-receptor antagonist, with a prolonged elimination half-life of over 9 h.

  14. Development of an in-line HPLC fingerprint ion-trap mass spectrometric method for identification and quality control of Radix Scrophulariae.

    Science.gov (United States)

    Jing, Jing; Chan, Chi-on; Xu, Lijia; Jin, Dengping; Cao, Xinwei; Mok, Daniel K W; Parekh, H S; Chen, Sibao

    2011-12-05

    Chromatographic fingerprinting has been widely accepted as a crucial method for qualitative and quantitative analyses of bioactives within traditional Chinese medicine. A fingerprint provides detailed information, specific for any given herb, thus facilitating the quality control measures of a given traditional Chinese medicine. In this article, quality assessment of Radix Scrophulariae was achieved by using high performance liquid chromatography combining diode-array detection and electrospray ionization mass spectrometry (HPLC-DAD-ESI/MS). Eight batches of sample obtained from different origins in China were used to establish the fingerprint and quantitative analyses. By comparing the retention times, UV and MS spectral data with reference standards, four characteristic peaks in the chromatograms were confirmed as corresponding to acetoside, angoroside C, cinnamic acid, and harpagoside. In addition, other two characteristic peaks were tentatively identified, following the literature interpretation of HPLC-ESI-MS and LC-MS/MS (affording structural information) to be sibirioside A and scrophuloside B(4), respectively. The results indicated that the newly developed HPLC-DAD-MS fingerprint method would be suitable for quality control of Radix Scrophulariae.

  15. Liquid chromatography-mass spectrometric method for the sensitive determination of niflumic acid in human plasma and its application to pharmacokinetic study of talniflumate tablet.

    Science.gov (United States)

    Park, Eun Ji; Na, Dong Hee; Shin, Young-Hee; Lee, Kang Choon

    2008-12-15

    A sensitive LC-MS method was developed and validated for the determination of niflumic acid (NFA), the active metabolite of the talniflumate formulation, in human plasma. The analyses were performed on C(18) column using acetonitrile-ammonium acetate buffer (pH 5.7, 40:60) as a mobile phase with quadrupole MS detection of NFA at m/z 281 in a negative ion-monitoring mode. Calibration curve was linear in the concentration range of 1-1000ng/mL in human plasma. The higher sensitivity of LC-MS allowed low concentrations of NFA to be determined at initial drug absorption and terminal elimination phases following oral administration of talniflumate tablet.

  16. Fluorinated carbon tag derivatization combined with fluorous solid-phase extraction: a new method for the highly sensitive and selective mass spectrometric analysis of glycans.

    Science.gov (United States)

    Li, Lulu; Jiao, Jing; Cai, Yan; Zhang, Ying; Lu, Haojie

    2015-01-01

    The sensitive and specific detection of glycans via mass spectrometry (MS) remains a significant challenge due to their low abundance in complex biological mixtures, inherent lack of hydrophobicity, and suppression by other, more abundant biological molecules (proteins/peptides) or contaminants. A new strategy for the sensitive and selective MS analysis of glycans based on fluorous chemistry is reported. Glycan reducing ends were derivatized with a hydrophobic fluorinated carbon tag, increasing glycan ionization efficiency during MS by more than an order of magnitude. More importantly, the fluorinated carbon tag enabled efficient fluorous solid-phase extraction (FSPE) to specifically enrich the glycans from contaminated solutions and protein mixtures. Finally, we successfully analyzed the N-glycome in human serum using this new method.

  17. Quantitation of donepezil and its active metabolite 6-O-desmethyl donepezil in human plasma by a selective and sensitive liquid chromatography-tandem mass spectrometric method

    Energy Technology Data Exchange (ETDEWEB)

    Patel, Bhavin N. [Chemistry Department, School of Sciences, Gujarat University, Navrangpura, Ahmedabad 380 009, Gujarat (India); Analytical Laboratory, BA Research India Ltd., Bodakdev, Ahmedabad 380 054, Gujarat (India); Sharma, Naveen [Analytical Laboratory, BA Research India Ltd., Bodakdev, Ahmedabad 380 054, Gujarat (India); Sanyal, Mallika [Chemistry Department, St. Xaviers' College, Navrangpura, Ahmedabad 380 009, Gujarat (India); Shrivastav, Pranav S. [Chemistry Department, School of Sciences, Gujarat University, Navrangpura, Ahmedabad 380 009, Gujarat (India)], E-mail: pranav_shrivastav@yahoo.com

    2008-11-23

    A sensitive and selective liquid chromatography-tandem mass spectrometry (LC-MS/MS) assay for the simultaneous determination of donepezil (D) and its pharmacologically active metabolite, 6-O-desmethyl donepezil (6-ODD) in human plasma is developed using galantamine as internal standard (IS). The analytes and IS were extracted from 500 {mu}L aliquots of human plasma via solid-phase extraction (SPE) on Waters Oasis HLB cartridges. Chromatographic separation was achieved in a run time of 6.0 min on a Waters Novapak C18 (150 mm x 3.9 mm, 4 {mu}m) column under isocratic conditions. Detection of analytes and IS was done by tandem mass spectrometry, operating in positive ion and multiple reaction monitoring (MRM) acquisition mode. The protonated precursor to product ion transitions monitored for D, 6-ODD and IS were at m/z 380.1 {yields} 91.2, 366.3 {yields} 91.3 and 288.2 {yields} 213.2, respectively. The method was fully validated for its selectivity, interference check, sensitivity, linearity, precision and accuracy, recovery, matrix effect, ion suppression/enhancement, cross-specificity, stability and dilution integrity. A linear dynamic range of 0.10-50.0 ng mL{sup -1} for D and 0.02-10.0 ng mL{sup -1} for 6-ODD was evaluated with mean correlation coefficient (r) of 0.9975 and 0.9985, respectively. The intra-batch and inter-batch precision (%CV, coefficient of variation) across five quality control levels was less than 7.5% for both the analytes. The method was successfully applied to a bioequivalence study of 10 mg donepezil tablet formulation in 24 healthy Indian male subjects under fasting condition.

  18. Immunoglobulin G (IgG) Fab glycosylation analysis using a new mass spectrometric high-throughput profiling method reveals pregnancy-associated changes.

    Science.gov (United States)

    Bondt, Albert; Rombouts, Yoann; Selman, Maurice H J; Hensbergen, Paul J; Reiding, Karli R; Hazes, Johanna M W; Dolhain, Radboud J E M; Wuhrer, Manfred

    2014-11-01

    The N-linked glycosylation of the constant fragment (Fc) of immunoglobulin G has been shown to change during pathological and physiological events and to strongly influence antibody inflammatory properties. In contrast, little is known about Fab-linked N-glycosylation, carried by ∼ 20% of IgG. Here we present a high-throughput workflow to analyze Fab and Fc glycosylation of polyclonal IgG purified from 5 μl of serum. We were able to detect and quantify 37 different N-glycans by means of MALDI-TOF-MS analysis in reflectron positive mode using a novel linkage-specific derivatization of sialic acid. This method was applied to 174 samples of a pregnancy cohort to reveal Fab glycosylation features and their change with pregnancy. Data analysis revealed marked differences between Fab and Fc glycosylation, especially in the levels of galactosylation and sialylation, incidence of bisecting GlcNAc, and presence of high mannose structures, which were all higher in the Fab portion than the Fc, whereas Fc showed higher levels of fucosylation. Additionally, we observed several changes during pregnancy and after delivery. Fab N-glycan sialylation was increased and bisection was decreased relative to postpartum time points, and nearly complete galactosylation of Fab glycans was observed throughout. Fc glycosylation changes were similar to results described before, with increased galactosylation and sialylation and decreased bisection during pregnancy. We expect that the parallel analysis of IgG Fab and Fc, as set up in this paper, will be important for unraveling roles of these glycans in (auto)immunity, which may be mediated via recognition by human lectins or modulation of antigen binding.

  19. Mass spectrometric thermodynamic studies of oxide systems and materials

    Science.gov (United States)

    Stolyarova, V. L.

    2016-01-01

    Progress in methods of synthesis of advanced materials as well as utilization of such materials at high temperatures requires information on the vaporization processes and thermodynamic properties of oxide systems. The optimal experimental method for these purposes is high-temperature mass spectrometry. This review summarizes and classifies experimental results obtained in mass spectrometric studies of the high-temperature thermodynamic properties of oxide systems and materials carried out in the last two decades. Published data on the vaporization processes and thermodynamic properties of oxide materials for high-temperature technologies are discussed from the standpoint of acid-base concept and model approaches including statistical thermodynamic methods. The bibliography includes 248 references.

  20. Determination of the Content of 1-Bromopropane in Textiles via Gas Chromatography-mass Spectrometric Method%气质联用法测定纺织品中1-溴丙烷的含量

    Institute of Scientific and Technical Information of China (English)

    林宁婷; 连秋燕; 邱丽君; 杨瑜榕

    2015-01-01

    In this paper a gas chromatography-mass spectrometric (GC-MS) method was established for the determination of 1-Bromopropane (1-BP) in textiles. 1-Bp in textiles was extracted by ultrasound with Acetone, the ultimate solution was analyzed by GC-MS under full-scan and selected-ion monitoring mode and quantiifed by external standard method. The results showed that, in the range of 0.5 mg/L~50.0 mg/L, the calibration curve was linear well with good correlation coefifcients (R>0.999);the detection limit was 0.5 mg/kg and the limit of quantitation was 1.0mg/kg;the average recovery was 82.0%~95.0%, and the relative standard deviations (RSD) were 3.1%~6.2%at three spiked concentration levels of 1.0, 2.0, 10mg/kg.%本文建立了纺织品中1-溴丙烷的气相色谱-质谱(GC-MS)检测方法。本方法中样品经丙酮超声提取后,采用气相色谱-质谱联用全扫描和选择离子扫描方式对提取液进行定性定量分析,外标法定量。结果表明:在0.5~50.0 mg/L范围内,方法的线性关系良好,相关系数达0.999以上;方法检测低限为0.5 mg/kg,定量限为1.0 mg/kg;在1.0、2.0和10.0 mg/kg 3个加标水平下,回收率为82.0%~95.0%,相对标准偏差3.1%~6.2%。

  1. Triacontyl modified silica gel as a sorbent for the preconcentration of polycyclic aromatic hydrocarbons in aqueous samples prior to gas chromatographic-mass spectrometry determination

    Institute of Scientific and Technical Information of China (English)

    Yan

    2010-01-01

    Triacontyl modified silica gel as a sorbent coupled with gas chromatography-mass spectrometry (GC-MS) was developed to determine EPA prior 16 polycyclic aromatic hydrocarbons (PAHs) in water samples. Various parameters of solid-phase extraction such as organic modifier solvent, eluent, sample flow rate and volume were optimized. The developed method was found to yield a linear calibration curve in the concentration range of 0.05-8 μg/L with respect to naphthalene, acenaphthylene, acenaphthene and 0.01-8μg/L for dibenz[a,h]anthracene and 0.05-14 μg/L for fluorene, phenanthrene, anthracene and 0.01-14 μg/L for the rest of analytes. Furthermore, the good accuracy and repeatability of the method made sure the requirements for achieving reliable analysis of PAHs in the environmental water samples, and the recoveries of optimal method were in the range of 80-120% except to higher volatility PAHs. C30-bonded silica was proved to be an efficient sorbent for extraction of high molecular weight PAHs.

  2. Spectrometric mixture analysis: An unexpected wrinkle

    Indian Academy of Sciences (India)

    Robert De Levie

    2009-09-01

    The spectrometric analysis of a mixture of two chemically and spectroscopically similar compounds is illustrated for the simultaneous spectrometric determination of caffeine and theobromine, the primary stimulants in coffee and tea, based on their ultraviolet absorbances. Their analysis indicates that such measurements may need an unexpectedly high precision to yield accurate answers, because of an artifact of inverse cancellation, in which a small noise or drift signal is misinterpreted in terms of a concentration difference. The computed sum of the concentrations is not affected.

  3. The theoretical study of full spectrum analysis method for airborne gamma-ray spectrometric data%航空伽玛射线全能谱数据分析方法的理论研究

    Institute of Scientific and Technical Information of China (English)

    倪卫冲

    2011-01-01

    Spectra of airborne gamma-ray spectrometry was found to be the synthesis of spectral components of radioelement sources by analyzing the constitution of radioactive sources for airborne gamma-ray spectrometric survey and establishing the models of gamma-ray measurement. The mathematical equation for analysising airborne gamma-ray full spectrometric data can be expressed into matrix and related expansions were developed for the mineral resources exploration, environmental radiaction measurement, nuclear emergency monitoring, and so on. Theoretical study showed that the atmospheric radon could be directly computed by airborne gamma-ray spectrometric data with full spectrum analysis without the use of the accessional upward-looking detectors.%通过航空伽玛能谱测量的源项分析和测量模型建立,发现航空伽玛能谱测量谱是各种源项能谱成分的合成谱。对航空伽玛射线全能谱分析方法给出了其数学分析式,其通用式可表示为矩阵式,对于矿产勘查和核环境与核应急等不同的应用领域能表达成相应的展开式。理论研究表明,航空伽玛全谱法不需要附加的上测探测器,就可直接解决大气氡修正问题,还将具有较好的经济效益。

  4. Determination of cadmium and lead in human biological samples by spectrometric techniques: a review.

    Science.gov (United States)

    Lemos, Valfredo Azevedo; de Carvalho, Anaildes Lago

    2010-12-01

    The analysis of human biological samples, such as blood, urine, nails, and hair, is generally used for the verification of human exposure to toxic metals. In this review, various spectrometric methods for the determination of cadmium and lead in biological samples are discussed and compared. Several spectrometric techniques are presented and discussed with respect to various characteristics such as sensitivity, selectivity, and cost. Special attention is drawn to the procedures for digestion prior to the determination of cadmium and lead in hair, nails, blood, and urine.

  5. Spectrofluorimetric, Atomic Absorption Spectrometric and Spectrophotometric Determination of Some Fluoroquinolones

    Directory of Open Access Journals (Sweden)

    Hesham Salem

    2005-01-01

    Full Text Available Simple, accurate, sensitive and selective spectrofluorimetric, atomic absorption spectrometric and spectrophotometric methods are described for the quantitative determination of ten fluoroquinolones (amifloxacin, ciprofloxacin hydrochloride, difloxacin hydrochloride, enoxacin, enrofloxacin, lomefloxacin hydrochloride, levofloxacin, norfloxacin, ofloxacin and pefloxacin mesylate. The first method was a spectrofluorimetric method in which samples of the studied drugs in 0.1 N H2SO4 showed native fluorescence at 450 nm when excitation was at 290 nm. The calibration graph was rectilinear from 0.3-1.4 μg mL-1 (method I. Cobalt sulphate was used for precipitation of the ion associates formed from the reaction with the cited drugs. The formation and solubility of the solid complexes at the optimum conditions of pH and ionic strength values have been studied. The method depends on direct determination of the ions in the precipitate or indirect determination of the ions in the filtrate by atomic absorption spectroscopy. The optimum conditions for precipitation were carefully studied. Rectilinear calibration graphs were obtained in the range of 3-30 μg mL-1 for each of the investigated drugs. The molar ratios of the formed chelats were determined by Job's method and their association constants were also calculated (method II. Ammonium vanadate was used for the spectrophotometric determination of the selected fluoroquinolones by oxidation in sulphuric acid medium resulting in the development of a greenish blue colour measured at 766 nm which was attributed to the vanadium (IV produced by reduction of vanadium (V by the selected drugs. The optimum conditions for heating time, reagent concentration and sulphuric acid concentration were carefully studied. The accuracy and precision of the proposed method was confirmed by estimating five or six replicates within Beer's law limits were obtained in the range 10-40 μg mL-1 for each of the investigated drugs

  6. The analysis of comet mass spectrometric data

    Science.gov (United States)

    Balm, S. P.; Hare, J. P.; Kroto, H. W.

    1991-04-01

    The mass spectra from the Giotto PICCA experiment have been studied using computer simulations based on tabulated mass spectrometric data. It is shown that random mixtures of organic compounds give rise to mass spectra with peaks at about 45, 60, 75, and 90 amu; i.e., separated by about 15 amu. In particular it is shown that the products of Urey-Miller type experiments give mass spectra which can match the observed Giotto data closely. The analysis indicates that the material consists mainly of C/H/O/N (i.e., it is organic), but that the assignment to any well defined organic material is less certain. It is not clear that mass spectrometric studies of complex mixtures have the prospect of yielding this type of information without some form of preseparation.

  7. Spectrometric characteristics of polystyrene scintillation films

    CERN Document Server

    Astvatsaturov, A R; Gavalyan, V B; Gavalyan, V G

    1999-01-01

    The spectrometric characteristics of five types of polystyrene scintillation films with thicknesses of 10, 30, 50 and 80 mu m and of analogous 250 mu m thick plates irradiated with sup 2 sup 3 sup 9 Pu, sup 2 sup 3 sup 8 Pu and sup 2 sup 2 sup 6 Ra sources of alpha-particles have been studied. The prospects of utilization of scintillation films as radiators for detection of heavy charged particles and measurement of their energy was experimentally shown.

  8. Spectrometric Characterization of Active Geosynchronous Satellites

    Science.gov (United States)

    Bedard, D.; Monin, D.; Scott, R.; Wade, G.

    2012-09-01

    Spectrometric characterization of artificial space objects for the purposes of Space Situational Awareness (SSA) has demonstrated great potential since this technique was first reported at this conference over a decade ago. Yet, much scientific work remains to be done before this tool can be used reliably in an operational context. For example, a detailed study of the impacts of a dynamic illumination-object-sensor geometry during individual spectrometric observations has yet to be described. A thorough understanding of this last problem is considered critical if reflectance spectroscopy will be used to characterize active low Earth orbiting spacecraft, in which the Sun-object-sensor geometry varies considerably over the course of a few seconds, or to study space debris that have uncontrolled and varying attitude. It is with the above questions in mind that two observation campaigns were conducted. The first consisted in using small-aperture telescopes to obtain multi-color photometric light curves of active geosynchronous satellites over a wide range of phase angles. The second observation campaign was conducted at the Dominion Astrophysical Observatory (DAO) using the 1.8-metre Plaskett telescope and its Cassegrain spectrograph. The objective of this experiment was to gather time-resolved spectrometric measurements of active geosynchronous satellites as a function of phase angle. This class of satellites was selected because their attitude is controlled and can be estimated to a high level of confidence. This paper presents the two observation campaigns and provides a summary of the key results of this experiment.

  9. Targeted quantitative mass spectrometric immunoassay for human protein variants

    Directory of Open Access Journals (Sweden)

    Nedelkov Dobrin

    2011-04-01

    Full Text Available Abstract Background Post-translational modifications and genetic variations give rise to protein variants that significantly increase the complexity of the human proteome. Modified proteins also play an important role in biological processes. While sandwich immunoassays are routinely used to determine protein concentrations, they are oblivious to protein variants that may serve as biomarkers with better sensitivity and specificity than their wild-type proteins. Mass spectrometry, coupled to immunoaffinity separations, can provide an efficient mean for simultaneous detection and quantification of protein variants. Results Presented here is a mass spectrometric immunoassay method for targeted quantitative proteomics analysis of protein modifications. Cystatin C, a cysteine proteinase inhibitor and a potential marker for several pathological processes, was used as a target analyte. An internal reference standard was incorporated into the assay, serving as a normalization point for cystatin C quantification. The precision, linearity, and recovery characteristics of the assay were established. The new assay was also benchmarked against existing cystatin C ELISA. In application, the assay was utilized to determine the individual concentration of several cystatin C variants across a cohort of samples, demonstrating the ability to fully quantify individual forms of post-translationally modified proteins. Conclusions The mass spectrometric immunoassays can find use in quantifying specific protein modifications, either as a part of a specific protein biomarker discovery/rediscovery effort to delineate the role of these variants in the onset of the disease, progression, and response to therapy, or in a more systematic study to delineate and understand human protein diversity.

  10. Detection of formestane abuse by mass spectrometric techniques.

    Science.gov (United States)

    de la Torre, Xavier; Colamonici, Cristiana; Curcio, Davide; Jardines, Daniel; Molaioni, Francesco; Parr, Maria Kristina; Botrè, Francesco

    2014-01-01

    Formestane (4-hydroxy-androstenedione) is an aromatase inhibitor prohibited in sports and included, since 2004, in the list of prohibited substances updated yearly by the World Anti-Doping Agency (WADA). Since the endogenous production of formestane has been described, it is mandatory for the anti-doping laboratories to use isotope ratio mass spectrometry (IRMS) to establish the exogenous origin before issuing an adverse analytical finding. The described IRMS methods for formestane detection are time-consuming, requiring usually two consecutive liquid chromatographic sample purifications in order to have final extracts of adequate purity before the mass spectrometric analysis. After establishing a procedure for the determination of the origin of formestane by IRMS without the need of derivatization, and integrated in the overall analytical strategy of the laboratory for pseudo-endogenous steroids, a mass spectrometric analysis by gas chromatography-mass spectrometry (GC-MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS) of formestane metabolites was carried out in order to investigate whether other biomarkers of formestane abuse could be integrated in order to avoid time-consuming and expensive IRMS confirmations for formestane. From the metabolic studies performed, the inclusion of 3β,4α-dihydroxy-5α-androstan-17-one (4α-hydroxy-epiandosterone) in the routine GC-MS procedures has demonstrated to be diagnostic in order to reduce the number of unnecessary confirmations of the endogenous origin of formestane.

  11. Advances in Mass Spectrometric Tools for Probing Neuropeptides

    Science.gov (United States)

    Buchberger, Amanda; Yu, Qing; Li, Lingjun

    2015-07-01

    Neuropeptides are important mediators in the functionality of the brain and other neurological organs. Because neuropeptides exist in a wide range of concentrations, appropriate characterization methods are needed to provide dynamic, chemical, and spatial information. Mass spectrometry and compatible tools have been a popular choice in analyzing neuropeptides. There have been several advances and challenges, both of which are the focus of this review. Discussions range from sample collection to bioinformatic tools, although avenues such as quantitation and imaging are included. Further development of the presented methods for neuropeptidomic mass spectrometric analysis is inevitable, which will lead to a further understanding of the complex interplay of neuropeptides and other signaling molecules in the nervous system.

  12. Mass Spectrometric Studies of Oxides

    Science.gov (United States)

    Jacobson, Nathan S.

    2012-01-01

    Current studies at NASA Glenn on oxide thermodynamics are discussed. Previous studies on the vaporization of B2O3 in reducing atmospheres led to inconsistent studies when B was used as a reductant. It is shown that liquid B2O3 does not wet B and a clear phase separation was noted in the Knudsen cell. This problem was solved by using FeB and Fe2B to supply a different and constant activity of B. The thermodynamic data thus derived are compared to quantum chemical composite calculations. A major problem in high temperature mass spectrometry is the determination of accurate ionization cross sections, particularly for molecules. The method of Deutsch and Mark shows promise and some sample calculations are discussed. Finally current studies on the thermodynamics of rare earth silicates are discussed. Here the problems are obtaining a measurable signal from SiO2 vaporization and non-equilibrium vaporization. The use of a Ta reducing agent provides a stronger signal, which is related to silica activity. The Whitman-Motzfeld relation adapted to KEMS measurements is applied to obtain equilibrium pressures.

  13. Automated 96-well solid phase extraction and hydrophilic interaction liquid chromatography-tandem mass spectrometric method for the analysis of cetirizine (ZYRTEC) in human plasma--with emphasis on method ruggedness.

    Science.gov (United States)

    Song, Qi; Junga, Heiko; Tang, Yong; Li, Austin C; Addison, Tom; McCort-Tipton, Melanie; Beato, Brian; Naidong, Weng

    2005-01-05

    A high-throughput bioanalytical method based on automated sample transfer, automated solid phase extraction, and hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-MS/MS) analysis, has been developed for the determination of cetirizine, a selective H(1)-receptor antagonist. Deuterated cetirizine (cetirizine-d(8)) was synthesized as described and was used as the internal standard. Samples were transferred into 96-well plates using an automated sample handling system. Automated solid phase extraction was carried out using a 96-channel programmable liquid-handling workstation. Solid phase extraction 96-well plate on polymer sorbent (Strata X) was used to extract the analyte. The extracted samples were injected onto a Betasil silica column (50 x 3, 5 microm) using a mobile phase of acetonitrile-water-acetic acid-trifluroacetic acid (93:7:1:0.025, v/v/v/v) at a flow rate of 0.5 ml/min. The chromatographic run time is 2.0 min per injection, with retention time of cetirizine and cetirizine-d(8) both at 1.1 min. The system consisted of a Shimadzu HPLC system and a PE Sciex API 3000 or API 4000 tandem mass spectrometer with (+) ESI. The method has been validated over the concentration range of 1.00-1000 ng/ml cetirizine in human plasma, based on a 0.10-ml sample size. The inter-day precision and accuracy of the quality control (QC) samples demonstrated <3.0% relative standard deviation (R.S.D.) and <6.0% relative error (RE). Stability of cetirizine in stock solution, in plasma, and in reconstitution solution was established. The absolute extraction recovery was 85.8%, 84.5%, and 88.0% at 3, 40, and 800 ng/ml, respectively. The recovery for the internal standard was 84.1%. No adverse matrix effects were noticed for this assay. The automation of the sample preparation steps not only increased the analysis throughput, but also increased method ruggedness. The use of a stable isotope-labeled internal standard further improved the method ruggedness

  14. Spectrometric and Voltammetric Analysis of Urease – Nickel Nanoelectrode as an Electrochemical Sensor

    OpenAIRE

    Rene Kizek; Josef Zehnalek; Martin Adamek; Katerina Klosova; Ales Horna; Libuse Trnkova*; Michal Masarik; Dalibor Huska; Olga Krystofova; Vojtech Adam; Jan Hradecky; Jaromir Hubalek

    2007-01-01

    Urease is the enzyme catalyzing the hydrolysis of urea into carbon dioxide and ammonia. This enzyme is substrate- specific, which means that the enzyme catalyzes the hydrolysis of urea only. This feature is a basic diagnostic criterion used in the determination of many bacteria species. Most of the methods utilized for detection of urease are based on analysis of its enzyme activity - the hydrolysis of urea. The aim of this work was to detect urease indirectly by spectrometric method and dire...

  15. Characterization of tetanus toxin, neat and in culture supernatant, by electrospray mass spectrometry

    NARCIS (Netherlands)

    Baar, B.L.M. van; Hulst, A.G.; Roberts, B.; Wils, E.R.J.

    2002-01-01

    A method was developed for the liquid chromatographic-mass spectrometric (LC-MS) identification of extremely neurotoxic toxins. The method combines sample treatment in a safety containment and analysis of detoxified material in a common laboratory facility. The method was applied to the characteriza

  16. Evaluation of mass spectrometric techniques for characterization of engineered proteins

    DEFF Research Database (Denmark)

    Roepstorff, P; Schram, K H; Andersen, Jens S.;

    1995-01-01

    Mass spectrometric characterization of engineered proteins has been examined using bovine recombinant Acyl-CoA-Binding Protein (rACBP), [15N]-labeled rACBP, and a number of sequence variants of ACBP produced by site-directed mutagenesis. The mass spectrometric techniques include ESIMS and MALDIMS...... was obtained by LC-ESIMS and by direct mixture analysis by MALDIMS. The latter technique was favorable in terms of sensitivity and speed. A general strategy for mass spectrometric characterization of engineered proteins is suggested....

  17. The prediction of paper properties from spectrometric data with machine learning

    OpenAIRE

    Jakovac, Alen

    2011-01-01

    In this thesis we present a solution for the problem of predicting the chemical and physical properties of paper from spectrometric data. We used a data set that consists of over 1000 samples of paper. For each sample 15 chemical and physical properties and its near-infrared spectra were measured. We used the following machine learning methods to predict the properties of paper: linear regression, pace regression, a nearest neighbor-based model, regression trees, a support vector machine, ...

  18. Pharmacokinetic comparison of seven 8-methoxypsoralen brands

    DEFF Research Database (Denmark)

    Menne, T; Andersen, Klaus Ejner; Larsen, E;

    1981-01-01

    The pharmacokinetics of seven 8-MOP brands were evaluated in 7 volunteers using an incomplete bloc design. After a single oral dose the 8-MOP plasma level was followed for 3 hours. The plasma concentration was measured with a gas chromatographic - mass spectrometric method, using an isotopic dilu...... of joules required to clear the patients in various PUVA centers....

  19. Development and validation of highly selective screening and confirmatory methods for the qualitative forensic analysis of organic explosive compounds with high performance liquid chromatography coupled with (photodiode array and) LTQ ion trap/Orbitrap mass spectrometric detections (HPLC-(PDA)-LTQOrbitrap).

    Science.gov (United States)

    Xu, Xiaoma; Koeberg, Mattijs; Kuijpers, Chris-Jan; Kok, Eric

    2014-01-01

    An LTQ-Orbitrap FTMS is a new (hybrid) mass spectrometric (MS) analyzer. It allows for the acquisition of full scan MS(n) (n-stage fragmentations, n=1-n) spectra with the linear ion trap detector (LTQ) at high speed and/or with the Fourier Transform-detector (Orbitrap) with ultra high mass resolution (>60,000 at m/zphoto diode array (PDA) detection. Two methods for the forensic screening and confirmation of all common trace explosives in post-blast residues have been developed on this instrument using atmospheric pressure chemical ionization (APCI). In one run, the nitrogen-containing explosives are analyzed with the combination of "LC-(PDA)-APCI(-)-LTQ MS(2)/Orbitrap FTMS" (Method 1). In another run, peroxide explosives are analyzed with "LC-APCI(+)-LTQ MS(2)/Orbitrap FTMS" (Method 2). The performance of both methods has been validated according to procedures defined in the EU COMMISSION DECISION implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of results (DC 2002/657/EC) and other standards (NEN 17025 and NEN 7777). The methods are highly selective due to the simultaneous utilization of the Orbitrap FTMS and LTQ MS(2), both of which are highly selective detectors Tested explosive compounds can be detected in the molecular ion form by the Orbitrap analyzer with minimal mass interference in different matrices when using an extremely narrow mass tolerance detection window (≤2ppm). The identification of a detected compound follows an identification point system. Experimental results show that almost all explosive compounds meet the confirmation criteria (minimum 4 points) required for the positive identification by the DC 2002/657/EC.

  20. Surface acoustic wave nebulization facilitating lipid mass spectrometric analysis.

    Science.gov (United States)

    Yoon, Sung Hwan; Huang, Yue; Edgar, J Scott; Ting, Ying S; Heron, Scott R; Kao, Yuchieh; Li, Yanyan; Masselon, Christophe D; Ernst, Robert K; Goodlett, David R

    2012-08-07

    Surface acoustic wave nebulization (SAWN) is a novel method to transfer nonvolatile analytes directly from the aqueous phase to the gas phase for mass spectrometric analysis. The lower ion energetics of SAWN and its planar nature make it appealing for analytically challenging lipid samples. This challenge is a result of their amphipathic nature, labile nature, and tendency to form aggregates, which readily precipitate clogging capillaries used for electrospray ionization (ESI). Here, we report the use of SAWN to characterize the complex glycolipid, lipid A, which serves as the membrane anchor component of lipopolysaccharide (LPS) and has a pronounced tendency to clog nano-ESI capillaries. We also show that unlike ESI SAWN is capable of ionizing labile phospholipids without fragmentation. Lastly, we compare the ease of use of SAWN to the more conventional infusion-based ESI methods and demonstrate the ability to generate higher order tandem mass spectral data of lipid A for automated structure assignment using our previously reported hierarchical tandem mass spectrometry (HiTMS) algorithm. The ease of generating SAWN-MS(n) data combined with HiTMS interpretation offers the potential for high throughput lipid A structure analysis.

  1. Gamma Spectrometric Analysis of Iron Ore Samples of Arak, Iran

    Directory of Open Access Journals (Sweden)

    Reza Pourimani

    2016-09-01

    Full Text Available Introduction Iron ore is one of the most important natural raw materials that is widely used for manufacturing iron and steel. This type of ore contains various amounts of radionuclides; thus, exposing workers handling their extraction, transportation, and processing to radiation. Materials and Methods In this study, 12 ore samples (each mass weighing about 2 kg were collected from the iron ore mining areas of Arak region, Iran. The specific activities of 226Ra, 232Th, and 40K were determined usinggamma-ray spectrometry method employing high-purity germanium (HPGe detector. Results The specific activities of 226Ra, 232Th, and 40K in samples were 9.39-271.70 Bq/kg, -3 Sv/y suggested in International Commission of Radiological Protection (ICRP Publication 82. Conclusion The gamma ray spectrometric analysis showed that the specific activities of natural radionuclides in samples, except for limonite ore, were within the worldwide range. The effective dose received by workers was much lower than the maximum acceptable value (1000 μSv/y; therefore, the level of radiations in this mine had no adverse consequences for public health.

  2. Comparison of serum copper determination by colorimetric and atomic absorption spectrometric methods in seven different laboratories. The S.F.B.C. (Société Française de Biologie Clinique) Trace Element Group.

    Science.gov (United States)

    Arnaud, J; Chappuis, P; Zawislak, R; Houot, O; Jaudon, M C; Bienvenu, F; Bureau, F

    1993-02-01

    An interlaboratory collaborative trial was conducted on the determination of serum copper using two different methods, based on colorimetry (test combination Copper, Boehringer Mannheim, Mannheim, Germany) and flame atomic absorption spectrometry (FAAS). The general performance of the colorimetric method was below that of FAAS, except for sensitivity and linear range, as assessed by detection limit (0.44 versus 1.32 mumol/L) and upper limit of linearity (150 versus 50 mumol/L). The range of the between-run CVs and the recovery of standard additions were, respectively, 2.3-11.9% and 92-127% for the colorimetric method and 1.1-6.0% and 93-101% for the FAAS method. Interferences were minimal with both methods. The two techniques correlated satisfactorily (the correlation coefficients ranged from 0.945-0.970 among laboratories) but the colorimetric assay exhibited slightly higher results than the FAAS method. Each method was transferable among laboratories.

  3. Liquid chromatography-mass spectrometric and liquid chromatography-tandem mass spectrometric determination of hallucinogenic indoles psilocin and psilocybin in "magic mushroom" samples.

    Science.gov (United States)

    Kamata, Tooru; Nishikawa, Mayumi; Katagi, Munehiro; Tsuchihashi, Hitoshi

    2005-03-01

    Accurate and sensitive analytical methods for psilocin (PC) and psilocybin (PB), tryptamine-type hallucinogens contained in "magic mushrooms," were investigated using liquid chromatography-mass spectrometry (LC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS-MS). The chromatographic separation on an ODS column and mass spectral information gave complete discrimination between PC and PB without derivatization. The mass spectrometric detection had a high sensitivity, and the tandem mass spectrometric detection provided more specificity and accuracy, as well as high sensitivity. The detection limits ranged from 1 to 25 pg by LC-MS in the selected ion monitoring mode, and the intra- and inter-day coefficients of variation were estimated to be 4.21-5.93% by LC-MS-MS in the selected reaction monitoring mode. By applying the present LC-MS-MS technique to four real samples, the contents of PC and PB were found to vary over a wide range (0.60-1.4 and 0.18-3.8 mg/g dry wt. for PC and PB, respectively) between samples.

  4. Single-laboratory validation of a high-performance liquid chromatographic-diode array detector-fluorescence detector/mass spectrometric method for simultaneous determination of water-soluble vitamins in multivitamin dietary tablets.

    Science.gov (United States)

    Chen, Pei; Atkinson, Renata; Wolf, Wayne R

    2009-01-01

    The purpose of this study was to develop a single-laboratory validated (SLV) method using high-performance liquid chromatography with different detectors [diode array detector (DAD); fluorescence detector (FLD); and mass spectrometry (MS)] for determination of 7 B-complex vitamins (B1-thiamin, B2-riboflavin, B3-nicotinamide, B6-pyridoxine, B9-folic acid, pantothenic acid, and biotin) and vitamin C in multivitamin/multimineral dietary supplements. The method involves the use of a reversed-phase octadecylsilyl column (4 microm, 250 x 2.0 mm id) and a gradient mobile phase profile. Gradient elution was performed at a flow rate of 0.25 mL/min. After a 5 min isocratic elution at 100% A (0.1% formic acid in water), a linear gradient to 50% A and 50% B (0.1% formic acid in acetonitrile) at 15 min was employed. Detection was performed with a DAD as well as either an FLD or a triple-quadrupole MS detector in the multiple reaction monitoring mode. SLV was performed using Standard Reference Material (SRM) 3280 Multivitamin/Multimineral Tablets, being developed by the National Institute of Standards and Technology, with support by the Office of Dietary Supplements of the National Institutes of Health. Phosphate buffer (10 mM, pH 2.0) extracts of the NIST SRM 3280 were analyzed by the liquid chromatographic (LC)-DAD-FLDIMS method. Following extraction, the method does not require any sample cleanup/preconcentration steps except centrifugation and filtration.

  5. Optimization of an anion-exchange high performance liquid chromatography-inductively coupled plasma-mass spectrometric method for the speciation analysis of oxyanion-forming metals and metalloids in leachates from cement-based materials.

    Science.gov (United States)

    Mulugeta, Mesay; Wibetoe, Grethe; Engelsen, Christian J; Lund, Walter

    2010-10-01

    A method was developed for the speciation analysis of the oxyanions of As(III), As(V), Cr(VI), Mo(VI), Sb(III), Sb(V), Se(IV), Se(VI) and V(V) in leachates from cement-based materials, based on anion-exchange HPLC coupled with ICP-MS. The method was optimized in a two-step multivariate approach: the effect of sample pH and mobile phase composition on resolution, peak symmetry and analysis time was studied. Optimum conditions were then identified for the significant experimental factors by studying their interdependence. A mobile phase composition of 20 mM ammonium nitrate, 50 mM ammonium tartrate and pH 9.5 was found to be a compromise optimum for the separation of the target analytes using isocratic elution. The optimum condition provided separation of the analytes in less than 6 min, at a mobile phase flow rate of 1.0 mL/min. The signal intensities of the analytes were improved by adding 1% methanol to the mobile phase. The limit of detection of the method was in the range 0.2-2.2 μg/L for the various species. The effect of sample constituents was studied using spiked concrete leachates. The method was used to determine the target oxyanionic species in leachates generated from a concrete material in the pH range 3.5-12.4; CrO(4)(2-), MoO(4)(2-) and VO(4)(3-) were detected in most of the leachates.

  6. Validation and use of a QuEChERS-based gas chromatographic-tandem mass spectrometric method for multiresidue pesticide analysis in blackcurrants including studies of matrix effects and estimation of measurement uncertainty.

    Science.gov (United States)

    Walorczyk, Stanisław

    2014-03-01

    A triple quadrupole GC-QqQ-MS/MS method was optimized for multiresidue analysis of over 180 pesticides in blackcurrants. The samples were prepared by using a modified quick, easy, cheap, effective, rugged and safe (QuEChERS) analytical protocol. To reduce matrix co-extractives in the final extract, the supernatant was cleaned up by dispersive-solid phase extraction (dispersive-SPE) with a mixture of sorbents: primary secondary amine (PSA), octadecyl (C18) and graphitized carbon black (GCB). The validation results demonstrated fitness for purpose of the streamlined method. The overall recoveries at the three spiking levels of 0.01, 0.05 and 0.2 mg kg(-1) spanned between 70% and 116% (102% on average) with relative standard deviation (RSD) values between 3% and 19% except for chlorothalonil (23%). Response linearity was studied in the range between 0.005 and 0.5 mg kg(-1). The matrix effect for each individual compound was evaluated through the study of ratios of the slopes obtained in solvent and blackcurrant matrix. The optimized method provided small matrix effect (30%, respectively. Following the application of "top-down" approach, the expanded measurement uncertainty was estimated as being 21% on average (coverage factor k=2, confidence level 95%). If compared with samples of other crops, the analyses of blackcurrants revealed a high percentage of exceedance of the legislative maximum residue levels (MRLs), as well as some instances of the detection of pesticides unapproved on this crop.

  7. Development of an achiral supercritical fluid chromatography method with ultraviolet absorbance and mass spectrometric detection for impurity profiling of drug candidates. Part II. Selection of an orthogonal set of stationary phases.

    Science.gov (United States)

    Lemasson, Elise; Bertin, Sophie; Hennig, Philippe; Boiteux, Hélène; Lesellier, Eric; West, Caroline

    2015-08-21

    Impurity profiling of organic products that are synthesized as possible drug candidates requires complementary analytical methods to ensure that all impurities are identified. Supercritical fluid chromatography (SFC) is a very useful tool to achieve this objective, as an adequate selection of stationary phases can provide orthogonal separations so as to maximize the chances to see all impurities. In this series of papers, we have developed a method for achiral SFC-MS profiling of drug candidates, based on a selection of 160 analytes issued from Servier Research Laboratories. In the first part of this study, focusing on mobile phase selection, a gradient elution with carbon dioxide and methanol comprising 2% water and 20mM ammonium acetate proved to be the best in terms of chromatographic performance, while also providing good MS response [1]. The objective of this second part was the selection of an orthogonal set of ultra-high performance stationary phases, that was carried out in two steps. Firstly, a reduced set of analytes (20) was used to screen 23 columns. The columns selected were all 1.7-2.5μm fully porous or 2.6-2.7μm superficially porous particles, with a variety of stationary phase chemistries. Derringer desirability functions were used to rank the columns according to retention window, column efficiency evaluated with peak width of selected analytes, and the proportion of analytes successfully eluted with good peak shapes. The columns providing the worst performances were thus eliminated and a shorter selection of columns (11) was obtained. Secondly, based on 160 tested analytes, the 11 columns were ranked again. The retention data obtained on these columns were then compared to define a reduced set of the best columns providing the greatest orthogonality, to maximize the chances to see all impurities within a limited number of runs. Two high-performance columns were thus selected: ACQUITY UPC(2) HSS C18 SB and Nucleoshell HILIC.

  8. Fast and simple procedure for liquid-liquid extraction of 136 analytes from different drug classes for development of a liquid chromatographic-tandem mass spectrometric quantification method in human blood plasma.

    Science.gov (United States)

    Remane, Daniela; Meyer, Markus R; Peters, Frank T; Wissenbach, Dirk K; Maurer, Hans H

    2010-07-01

    In clinical and forensic toxicology, different extraction procedures as well as analytical methods are used to monitor different drug classes of interest in biosamples. Multi-analyte procedures are preferable because they make the analytical strategy much simpler and cheaper and allow monitoring of analytes of different drug classes in one single body sample. For development of such a multi-analyte liquid chromatography-tandem mass spectrometry approach, a rapid and simple method for the extraction of 136 analytes from the following drug classes has been established: antidepressants, neuroleptics, benzodiazepines, beta-blockers, oral antidiabetics, and analytes relevant in the context of brain death diagnosis. Recovery, matrix effects, and process efficiency were tested at two concentrations using six different lots of blank plasma. The recovery results obtained using absolute peak areas were compared with those calculated using area ratios analyte/internal standard. The recoveries ranged from 8% to 84% for antidepressants, from 10% to 79% for neuroleptics, from 60% to 81% for benzodiazepines, from 1% to 71% for beta-blockers, from 10% to 73% for antidiabetics, and from 60% to 86% for analytes relevant in the context of brain death diagnosis. With the exception of 52 analytes at low concentration and 37 at high concentration, all compounds showed recoveries with acceptable variability with less than 15% and 20% coefficients of variation. Recovery results obtained by comparing peak area ratios were nearly the same, but 35 analytes at low concentration and 17 at high concentration lay above the acceptance criteria. Matrix effects with more than 25% were observed for 18 analytes. The results were acceptable for 119 analytes at high concentrations.

  9. Assessment of current mass spectrometric workflows for the quantification of low abundant proteins and phosphorylation sites

    Directory of Open Access Journals (Sweden)

    Manuel Bauer

    2015-12-01

    Full Text Available The data described here provide a systematic performance evaluation of popular data-dependent (DDA and independent (DIA mass spectrometric (MS workflows currently used in quantitative proteomics. We assessed the limits of identification, quantification and detection for each method by analyzing a dilution series of 20 unmodified and 10 phosphorylated synthetic heavy labeled reference peptides, respectively, covering six orders of magnitude in peptide concentration with and without a complex human cell digest background. We found that all methods performed very similarly in the absence of background proteins, however, when analyzing whole cell lysates, targeted methods were at least 5–10 times more sensitive than directed or DDA methods. In particular, higher stage fragmentation (MS3 of the neutral loss peak using a linear ion trap increased dynamic quantification range of some phosphopeptides up to 100-fold. We illustrate the power of this targeted MS3 approach for phosphopeptide monitoring by successfully quantifying 9 phosphorylation sites of the kinetochore and spindle assembly checkpoint component Mad1 over different cell cycle states from non-enriched pull-down samples. The data are associated to the research article ‘Evaluation of data-dependent and data-independent mass spectrometric workflows for sensitive quantification of proteins and phosphorylation sites׳ (Bauer et al., 2014 [1]. The mass spectrometry and the analysis dataset have been deposited to the ProteomeXchange Consortium (http://proteomecentral.proteomexchange.org via the PRIDE partner repository with the dataset identifier PXD000964.

  10. Rapid headspace solid-phase microextraction-gas chromatographic-time-of-flight mass spectrometric method for qualitative profiling of ice wine volatile fraction. II: Classification of Canadian and Czech ice wines using statistical evaluation of the data.

    Science.gov (United States)

    Setkova, Lucie; Risticevic, Sanja; Pawliszyn, Janusz

    2007-04-20

    The previously developed and optimized headspace solid-phase microextraction (HS-SPME)-GC-time-of-flight (TOF) MS analytical method for the determination of compounds with a wide range of polarities and volatilities was successfully used in this study to characterize and classify a large set of ice wines according to their origin, grape variety and oak or stainless steel fermentation/ageing conditions, based on a statistical evaluation (principal component analysis (PCA)) of the measured data. More than 130 ice wine samples collected directly from Canadian and Czech wine producers were analyzed in this study. The SPME step was beneficially carried out utilizing the new-generation super elastic divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) 50 microm/30 microm fiber assembly. One fiber was used for the whole sequence of ice wine samples, control and blank experiments, which consisted of more than 600 individual extraction/injection cycles. Utilizing the high-speed TOF analyzer, full spectral information within the range of 35-450 u was collected for the entire GC run (as short as 4.5 min) without compromising in the detection sensitivity, as compared to other scanning mass analyzers operated in selected ion monitoring or MS(n) mode to achieve similar sensitivity. The identification of analytes was performed by a combination of the linear temperature-programmed retention index (LTPRI) approach with the comparison of the obtained spectra with three libraries included in the ChromaTOF software. A total of 201 peaks were tentatively assigned as ice wine aroma components and 58 of those compounds were evaluated in all of the examined samples.

  11. High-throughput sequential injection method for simultaneous determination of plutonium and neptunium in environmental solids using macroporous anion-exchange chromatography, followed by inductively coupled plasma mass spectrometric detection.

    Science.gov (United States)

    Qiao, Jixin; Hou, Xiaolin; Roos, Per; Miró, Manuel

    2011-01-01

    This paper reports an automated analytical method for rapid and simultaneous determination of plutonium and neptunium in soil, sediment, and seaweed, with detection via inductively coupled plasma mass spectrometry (ICP-MS). A chromatographic column packed with a macroporous anion exchanger (AG MP-1 M) was incorporated in a sequential injection (SI) system for the efficient retrieval of plutonium, along with neptunium, from matrix elements and potential interfering nuclides. The sorption and elution behavior of plutonium and neptunium onto AG MP-1 M resin was compared with a commonly utilized AG 1-gel-type anion exchanger. Experimental results reveal that the pore structure of the anion exchanger plays a pivotal role in ensuring similar separation behavior of plutonium and neptunium along the separation protocol. It is proven that plutonium-242 ((242)Pu) performs well as a tracer for monitoring the chemical yield of neptunium when using AG MP-1 M resin, whereby the difficulties in obtaining a reliable and practicable isotopic neptunium tracer are overcome. An important asset of the SI setup is the feasibility of processing up to 100 g of solid substrates using a small-sized (ca. 2 mL) column with chemical yields of neptunium and plutonium being ≥79%. Analytical results of three certified/standard reference materials and two solid samples from intercomparison exercises are in good agreement with the reference values at the 0.05 significance level. The overall on-column separation can be completed within 3.5 h for 10 g of soil samples. Most importantly, the anion-exchange mini-column suffices to be reused up to 10-fold with satisfactory chemical yields (>70%), as demanded in environmental monitoring and emergency scenarios, making the proposed automated assembly well-suited for unattended and high-throughput analysis.

  12. Comparison of two derivatization-based methods for solid-phase microextraction-gas chromatography-mass spectrometric determination of bisphenol A, bisphenol S and biphenol migrated from food cans.

    Science.gov (United States)

    Viñas, P; Campillo, N; Martínez-Castillo, N; Hernández-Córdoba, M

    2010-05-01

    An environmentally friendly sample pretreatment system based on solid-phase microextraction (SPME) for the sensitive determination of bisphenol A (BPA), bisphenol S (BPS) and biphenol (BP) is described. Two derivatisation reactions to obtain volatile derivatives are compared. Derivatisation with acetic anhydride (AA) was performed in situ in a 5-mM Na(2)CO(3)/NaHCO(3) buffer solution and analytes were extracted by direct immersion (DI) using a PA fibre (85 microm) at 90 degrees C for 40 min with stirring at 1,500 rpm. For derivatisation with bis-(trimethylsilyl)trifluoroacetamide (BSTFA), the analytes were first extracted by DI using the PA fibre at 70 degrees C for 40 min with stirring at 500 rpm. The fibre was then removed, dried in a nitrogen stream for 2 min and introduced into the headspace of BSTFA at 50 degrees C for 30 s. After derivatisation, the analytes were desorbed in the injection port of the GC in the splitless mode at 280 degrees C for 4 min. The separation was carried out by coupling gas chromatography with mass spectrometry in the selected ion monitoring mode, GC-MS(SIM). The method allowed the determination of the migrating levels of bisphenols found in food cans, and it was validated for linearity, detection and quantitation limits, selectivity, accuracy and precision. Detection limits ranged from 3 to 16 pg mL(-1), depending on the compound, at a signal-to-noise ratio of 3. Recoveries obtained for spiked samples were satisfactory for all compounds. Levels of BPA were higher than those of BPS and the lowest contents were found for BP.

  13. [Health state evaluation of power-shift steering transmission using PCA-AHP methodology based on spectrometric oil analysis].

    Science.gov (United States)

    Zhang, Ying-Feng; Ma, Biao; Zheng, Chang-Song; Zhang, Jin-Le; Fan, Yu-Heng

    2010-04-01

    Spectrometric oil analysis is an important method to study the running state of power-shift steering transmission (PSST). An evaluation model of PSST health state was developed on the basis of the theories of principal component analysis (PCA) and analytic hierarchy process (AHP) using spectrometric oil analysis data. Considering the concept of mechanical equipment and wear elements in spectrometric oil analysis data, the health value was employed to quantitatively describe the running state degree of PSST, and the grades of health state were classified based on the health values. The oil analysis data were studied during the process of choosing principal components. The weight vectors of principal components were obtained by using the AHP method. In the course, the conformation of judgement matrix and the consistency check were also studied. The evaluation model was developed by combining the PCA and AHP methods. This model has been proved to have better accuracy in evaluating the running state of PSST. This work is important for developing state evaluation of PSST.

  14. Utility of spatially-resolved atmospheric pressure surface sampling and ionization techniques as alternatives to mass spectrometric imaging (MSI) in drug metabolism

    Energy Technology Data Exchange (ETDEWEB)

    Blatherwick, Eleanor Q. [University of Warwick, UK; Van Berkel, Gary J [ORNL; Pickup, Kathryn [AstraZeneca R& D Sweden; Johansson, Maria K. [AstraZeneca R& D Sweden; Beaudoin, Marie-Eve [AstraZeneca, USA; Cole, Roderic [ORNL; Day, Jennifer M. [AstraZeneca R& D, UK; Iverson, Suzanne [AstraZeneca R& D Sweden; Wilson, Ian D. [AstraZeneca R& D, UK; Scrivens, James H. [University of Warwick, UK; Weston, Daniel J. [AstraZeneca R& D, UK

    2011-01-01

    1. Tissue distribution studies of drug molecules play an essential role in the pharmaceutical industry and are commonly undertaken using quantitative whole body autoradiography (QWBA) methods. 2. The growing need for complementary methods to address some scientific gaps around radiography methods has led to increased use of mass spectrometric imaging (MSI) technology over the last 5 to 10 years. More recently, the development of novel mass spectrometric techniques for ambient surface sampling has redefined what can be regarded as fit-for-purpose for MSI in a drug metabolism and disposition arena. 3. Together with a review of these novel alternatives, this paper details the use of two liquid microjunction (LMJ)- based mass spectrometric surface sampling technologies. These approaches are used to provide qualitative determination of parent drug in rat liver tissue slices using liquid extraction surface analysis (LESA) and to assess the performance of a LMJ surface sampling probe (LMJ-SSP) interface for quantitative assessment of parent drug in brain, liver and muscle tissue slices. 4. An assessment of the utility of these spatially-resolved sampling methods is given, showing interdependence between mass spectrometric and QWBA methods, in particular there emerges a reason to question typical MSI workflows for drug metabolism; suggesting the expedient use of profile or region analysis may be more appropriate, rather than generating time-intensive molecular images of the entire tissue section.

  15. Quantitative analysis of flavonols, flavones, and flavanones in fruits, vegetables and beverages by high-performance liquid chromatography with photo-diode array and mass spectrometric detection

    DEFF Research Database (Denmark)

    Justesen, U.; Knuthsen, Pia; Leth, Torben

    1998-01-01

    A high-performance liquid chromatographic (HPLC) separation method viith photo-diode array (PDA) and mass spectrometric (MS) detection was developed to determine and quantify flavonols, flavones, and flavanones in fruits, vegetables and beverages. The compounds were analysed as aglycones, obtained...

  16. The 3D inversion of airborne gamma-ray spectrometric data

    Science.gov (United States)

    Minty, Brian; Brodie, Ross

    2016-07-01

    We present a new method for the inversion of airborne gamma-ray spectrometric line data to a regular grid of radioelement concentration estimates on the ground. The method incorporates the height of the aircraft, the 3D terrain within the field of view of the spectrometer, the directional sensitivity of rectangular detectors, and a source model comprising vertical rectangular prisms with the same horizontal dimensions as the required grid cell size. The top of each prism is a plane surface derived from a best-fit plane to the digital elevation model of the earth's surface within each grid cell area. The method is a significant improvement on current methods, and gives superior interpolation between flight lines. It also eliminates terrain effects that would normally remain in the data after the conventional processing of these data assuming a flat-earth model.

  17. Mass spectrometric detection, identification, and fragmentation of arseno-phytochelatins.

    Science.gov (United States)

    Schmied-Tobies, Maria I H; Arroyo-Abad, Uriel; Mattusch, Jürgen; Reemtsma, Thorsten

    2014-11-01

    Phytochelatins (PC) are cystein-rich oligopeptides in plants for coordination with toxic metals and metalloids via their thiol groups. The composition, structure, and mass spectrometric fragmentation of arseno-PC (As-PC) with PC of different degree of oligomerization (PC2-PC5) in solution were studied using liquid chromatography coupled in parallel to inductively coupled plasma mass spectrometry and electrospray ionization quadrupole time-of-flight mass spectrometry. As-PC were detected from As(PC2) to As(PC5) with an increasing number of isomers that differ in the position of thiol groups bound to As. Thermodynamic modeling supported the identification process in case of these isomers. Mass spectrometric fragmentation of the As-PC does not follow the established pattern of peptides but is governed by the formation of series of As-containing annular cations, which coordinate to As via S, N, or O. Structure proposals for 30 As-PC fragment ions in the range m/z 147.92 to m/z 1290.18 are elaborated. Many of these fragment ions are characteristic to several As-PC and may be suited for a screening for As-PC in plant extracts. The mass spectrometric data offer the perspective for a future more sensitive determination of As-PC by means of liquid chromatography tandem mass spectrometry with multiple reaction monitoring.

  18. 固相萃取-色谱质谱技术在毒物筛查中的应用进展%Progress of Solid-phase Extraction Coupled with Chromatograph-Mass Spectrum in Toxicological Screening

    Institute of Scientific and Technical Information of China (English)

    张泽楠; 常靖; 王芳琳; 于忠山; 张云峰; 崔冠峰

    2015-01-01

    固相萃取是近年发展起来的一种样品前处理技术,主要用于样品的分离和富集,能够将生物检材中的目标待测物有效的与杂质组分分离,具有较高的回收率,其样品预处理过程简单,操作便捷。在法庭科学领域,可根据生物检材,如生物体液、组织、毛发等基质的性质,选择相应的固相萃取方法;同时亦可根据目标待测物,如目标待测物的酸碱性,选用不同的固相萃取方法。色谱法是一种分离和分析方法,它利用不同物质在不同相态的选择性分配,使混合物中的不同组分根据其性质不同而分离。质谱法在分析中可提供丰富的结构信息。固相萃取-色谱质谱联用技术集固相萃取与色谱质谱检测技术优点于一体,可实现对复杂基质中的特定毒物与非特定毒物进行高效萃取、净化与检测,具有检材消耗少、检测速度快、灵敏度高等特点,已被广泛应用于环境监测、药物分析、法庭科学领域等,成为当前毒物筛查的重要手段,具有选择性好、灵敏度高、基质效应低等特点,且易实现在线分析,特别适用于法庭毒物分析中单一毒物或多种毒物的筛查。本文综述了固相萃取-色谱质谱联用技术在法庭科学毒物毒品分析中的应用进展,以供同行参考。%Solid-phase extraction (SPE) is one of sample pretreatment technologies developed in recent years, which separates target compounds from biological complex matrixes and impurity by using the sorbent absorption. The sample pretreatment process of SPE is simple and convenient, which has been widely used in pharmaceutical analysis, food testing, environment monitoring, forensic science and other fields. Solid-phase extraction can separate target substance from complex matrix with high recovery, which makes it play an important role in the field of forensic science. As the method for separation and analysis

  19. Evaluation of Chemical Analysis Method and Determination of Polycyclic Aromatic Hydrocarbons Content from Seafood and Dairy Products

    OpenAIRE

    Lee, So-Young; Lee, Jee-Yeon; Shin, Han-Seung

    2015-01-01

    This study was carried out to investigate contents of 8 polycyclic aromatic hydrocarbons (PAHs) from frequently consumed seafood and dairy products and to evaluate their chemical analysis methods. Samples were collected from markets of 9 cities in Korea chosen as the population reference and evaluated. The methodology involved saponification, extraction with n-hexane, clean-up on Sep-Pak silica cartridges and gas chromatograph-mass spectrometry analysis. Validation proceeded on 2 matrices. Re...

  20. Gamma-spectrometric surveys in differentiated granites. I: a review of the method and of the geochemical behavior of K, Th and U; Levantamentos gamaespectrometricos em granitos diferenciados. I: revisao da metodologia e do comportamento geoquimico dos elementos K, Th e U

    Energy Technology Data Exchange (ETDEWEB)

    Ulbrich, Horstpeter Herberto Gustavo Jose; Ulbrich, Mabel Norma Costas [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Geociencias. Dept. de Mineralogia e Geotectonica], e-mail: hulbrich@usp.br, e-mail: mulbrich@usp.br; Ferreira, Francisco Jose Fonseca [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Dept. de Geologia. Lab. de Pesquisas em Geofisica Aplicada; Alves, Luizemara Soares [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil)], e-mail: luizemara@petrobras.com.br; Guimaraes, Gilson Burigo [Universidade Estadual de Ponta Grossa (UEPG), PR (Brazil). Dept. de Geociencias], e-mail: gburigo@ig.com.br; Fruchting, Allan [Votorantim Metais, Sao Paulo, SP (Brazil)], e-mail: allan.fruchting@vmetais.com.br

    2009-07-01

    This contribution is part of a research project on the Neo proterozoic Cunhaporanga Granitic Complex (CGC), cropping out in the Ponta Grossa Arch (Parana state, SE Brazil). An initial study used the gamma-spectrometric data of the Serra do Mar Sul Aero geophysical Project, performed during the 70's for CPRM. Later, terrestrial gamma-spectrometric surveys focused on the study of the differentiated Joaquim Murtinho Granite (JMG) in the NW corner of CGC, and the Serra do Carambei Granite, to the SW. In this paper, the results obtained for JMG are presented in two parts. The first deals with methodology and the presentation of several gamma-spectrometric 'color-scale' maps, indicating that results obtained in granites depend strongly on a climatic factor, given the mobility of K during weathering in subtropical climates with strong rainfalls, also favoring a greater mobility of U. Minerals that are U and Th hosts, documented in granites, are reviewed, together with the weathering processes that control the mobility of K, U and Th in soils. Strong K signals in granitic areas submitted to these climates document the presence of fresh rock and/or effects of hydrothermal alteration, while weak or nil signals are evidence of strong leaching of K during weathering. U and Th will be retained in the residual soils, in part leading to their selective enrichment, also coupled with soil migration to lower topographic levels by colluvial transport. The larger solubility of U (as uranyl ion) allows its liberation under oxidizing conditions, and its migration, limited by the possibility of absorption in newly formed mineral and organic soil phases. Th should be retained almost totally in resistant phases and, when liberated in solution, will mostly be fixed in organic and inorganic soil substances. (author)

  1. Separation Techniques for Uranium and Plutonium at Trace Levels for the Thermal Ionization Mass Spectrometric Determination

    Energy Technology Data Exchange (ETDEWEB)

    Suh, M. Y.; Han, S. H.; Kim, J. G.; Park, Y. J.; Kim, W. H

    2005-12-15

    This report describes the state of the art and the progress of the chemical separation and purification techniques required for the thermal ionization mass spectrometric determination of uranium and plutonium in environmental samples at trace or ultratrace levels. Various techniques, such as precipitation, solvent extraction, extraction chromatography, and ion exchange chromatography, for separation of uranium and plutonium were evaluated. Sample preparation methods and dissolution techniques for environmental samples were also discussed. Especially, both extraction chromatographic and anion exchange chromatographic procedures for uranium and plutonium in environmental samples, such as soil, sediment, plant, seawater, urine, and bone ash were reviewed in detail in order to propose some suitable methods for the separation and purification of uranium and plutonium from the safeguards environmental or swipe samples. A survey of the IAEA strengthened safeguards system, the clean room facility of IAEA's NWAL(Network of Analytical Laboratories), and the analytical techniques for safeguards environmental samples was also discussed here.

  2. Quantitative Mass Spectrometric Analysis and Post-Extraction Stability Assessment of the Euglenoid Toxin Euglenophycin

    Directory of Open Access Journals (Sweden)

    Paul V. Zimba

    2013-09-01

    Full Text Available Euglenophycin is a recently discovered toxin produced by at least one species of euglenoid algae. The toxin has been responsible for several fish mortality events. To facilitate the identification and monitoring of euglenophycin in freshwater ponds, we have developed a specific mass spectrometric method for the identification and quantitation of euglenophycin. The post-extraction stability of the toxin was assessed under various conditions. Euglenophycin was most stable at room temperature. At 8 °C there was a small, but statistically significant, loss in toxin after one day. These methods and knowledge of the toxin’s stability will facilitate identification of the toxin as a causative agent in fish kills and determination of the toxin’s distribution in the organs of exposed fish.

  3. Combination of electrochemical, spectrometric and other analytical techniques for high throughput screening of pharmaceutically active compounds.

    Science.gov (United States)

    Suzen, Sibel; Ozkan, Sibel A

    2010-08-01

    Recently, use of electrochemistry and combination of this method with spectroscopic and other analytical techniques are getting one of the important approaches in drug discovery and research as well as quality control, drug stability, determination of physiological activity, measurement of neurotransmitters. Many fundamental physiological processes are depending on oxido-reduction reactions in the body. Therefore, it may be possible to find connections between electrochemical and biochemical reactions concerning electron transfer pathways. Applications of electrochemical techniques to redox-active drug development and studies are one of the recent interests in drug discovery. In this review, the latest developments related to the use of electrochemical techniques in drug research in order to evaluate possible combination spectrometric methods with electrochemical techniques.

  4. Liquid chromatography-mass spectrometric determination of rufinamide in low volume plasma samples.

    Science.gov (United States)

    Gáll, Zsolt; Vancea, Szende; Dogaru, Maria T; Szilágyi, Tibor

    2013-12-01

    Quantification of rufinamide in plasma was achieved using a selective and sensitive liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method. The chromatographic separation was achieved on a reversed phase column (Zorbax SB-C18 100mm×3mm, 3.5μm) under isocratic conditions. The mobile phase consisted of a mixture of water containing 0.1% formic acid and methanol (50:50, v/v). The mass spectrometric detection of the analyte was in multiple reaction monitoring mode (MRM) using an electrospray positive ionization (ESI positive). The monitored ions were 127m/z derived from 239m/z rufinamide and 108m/z derived from 251m/z the internal standard (lacosamide). Protein precipitation with methanol was applied for sample preparation using only 50μl aliquots. The concentration range was 40-2000ng/ml for rufinamide in plasma. The limit of detection was 1.25ng/ml and the lower limit of quantification was established at 5ng/ml rufinamide concentration. Selectivity and matrix effect was verified using individual human, rat and rabbit plasma samples. Short-term, post-preparative and freeze-thaw stability was also investigated. The proposed method provides accuracy, precision and high-throughput (short runtime 4.5min) for quantitative determination of rufinamide in plasma. This is the first reported liquid chromatography-tandem mass spectrometric (LC-MS/MS) method for analysis of rufinamide from low volume plasma samples. The LC-MS/MS method was validated according to the current official guidelines and can be applied to accurately measure rufinamide level of large number of plasma samples from clinical studies or therapeutic drug monitoring.

  5. Study on the Inclusion Interactions of Cucurbit[7]uril with 6-Mercaptopurine and Adenine by Fluorescence Spectrometric Method%荧光光谱法研究葫芦[7]脲与6-巯嘌呤和腺嘌呤的包结作用

    Institute of Scientific and Technical Information of China (English)

    何小英; 李来生; 方奕珊; 陈红

    2012-01-01

    The inclusion interactions of cucurbit [7] uril (CB[7]) with 6-mercaptopurine (6-MP) and adenine(ADP) were studied by fluorescence spectrometric method. Several effect factors such as time, the pH value and temperature on the fluorescence intensity and the stability of the complex were investigated. The complex constants of CB[7] with 6-MP and ADP were determined according to the Benesi-Hildebrand equation,respectively. The results indicated that the pH value had a significant effect on the inclusion interactions. 6-MP and ADP had the optimal and stable excitation and emission wavelength as the pH value were 8. 0 for 6-MP and 2. 0 for ADP within 5 min. With the increasing of the concentrations of CB[7],the fluorescence of the two complexes increased obviously. The inclusion constants were 3. 6797× 102 L·mol-1 for 6-MP-CB[7] and 2. 2033 × 102 L·mol-1 for ADP-CB[7] at 298 K with the same inclusive ratio of It 1. The main interaction forces between CB[7] and the above purines were discussed based on the thermodynamic parameters. CB[7] is only well water-soluble superamolecules among cucurbituril family members, and has great potential as drug carriers with safety and low toxicity.%采用荧光光谱法分别研究了葫芦[7]脲(CB[7])对6-巯嘌呤(6-MP)和腺嘌呤(ADP)的包结作用.实验考察了时间、pH值以及温度对荧光强度和包结作用的影响,利用Benesi-Hildebrand方程分别计算出6-MP和ADP与CB[7]的包结常数.结果表明:酸度对体系的包结有明显的影响.在pH值为8.0和2.0左右时,6-MP和ADP分别具有稳定和最佳激发和发射波长,随着CB[7]浓度的增大,体系的荧光强度都有明显增强,包结作用迅速(小于5 min).实验得出CB[7]与6-MP和ADP的包结比均为1∶1,在298 K时的包结常数分别为3.6797×102 L·mol-1和2.2033×102 L·mo1-1.通过热力学参数的变化,探讨了维系包结物稳定性的主要作用力.CB[7]是葫芦脲家族中水溶性最强的主体分子,作为一种

  6. Mass spectrometric analysis of monolayer protected nanoparticles

    Science.gov (United States)

    Zhu, Zhengjiang

    Monolayer protected nanoparticles (NPs) include an inorganic core and a monolayer of organic ligands. The wide variety of core materials and the tunable surface monolayers make NPs promising materials for numerous applications. Concerns related to unforeseen human health and environmental impacts of NPs have also been raised. In this thesis, new analytical methods based on mass spectrometry are developed to understand the fate, transport, and biodistributions of NPs in the complex biological systems. A laser desorption/ionization mass spectrometry (LDI-MS) method has been developed to characterize the monolayers on NP surface. LDI-MS allows multiple NPs taken up by cells to be measured and quantified in a multiplexed fashion. The correlations between surface properties of NPs and cellular uptake have also been explored. LDI-MS is further coupled with inductively coupled plasma mass spectrometry (ICP-MS) to quantitatively measure monolayer stability of gold NPs (AuNPs) and quantum dots (QDs), respectively, in live cells. This label-free approach allows correlating monolayer structure and particle size with NP stability in various cellular environments. Finally, uptake, distribution, accumulation, and excretion of NPs in higher order organisms, such as fish and plants, have been investigated to understand the environmental impact of nanomaterials. The results indicate that surface chemistry is a primary determinant. NPs with hydrophilic surfaces are substantially less toxic and present a lower degree of bioaccumulation, making these nanomaterials attractive for sustainable nanotechnology.

  7. E-2-benzylidenebenzocyclanones. II. IR and mass spectrometric investigations

    Science.gov (United States)

    Tarczay, Gy; Vékey, K.; Ludányi, K.; Perjési, P.; Sohár, P.

    2000-03-01

    A series of E-2-benzylideneindanones (a) -tetralones (b) and -benzosuberones (c) with OCH 3 ( 2- 4), NO 2 ( 5- 7) and F ( 8- 10) substituents in ortho, meta or para position was studied by IR and mass spectrometry. The most important IR bands were assigned and stated correlations between some frequencies and the stereostructure or conjugation feature of the molecules investigated. IR spectra were also analyzed in order to find frequencies characteristic of the size of the alkanone ring. The mass spectrometric investigation aimed at determining fragmentation pathways and finding correlations between them and the ring size of the alkanone ring or the position of the substituents.

  8. Mass Spectrometric Detection of Bacterial Protein Toxins and Their Enzymatic Activity.

    Science.gov (United States)

    Kalb, Suzanne R; Boyer, Anne E; Barr, John R

    2015-08-31

    Mass spectrometry has recently become a powerful technique for bacterial identification. Mass spectrometry approaches generally rely upon introduction of the bacteria into a matrix-assisted laser-desorption time-of-flight (MALDI-TOF) mass spectrometer with mass spectrometric recognition of proteins specific to that organism that form a reliable fingerprint. With some bacteria, such as Bacillus anthracis and Clostridium botulinum, the health threat posed by these organisms is not the organism itself, but rather the protein toxins produced by the organisms. One such example is botulinum neurotoxin (BoNT), a potent neurotoxin produced by C. botulinum. There are seven known serotypes of BoNT, A-G, and many of the serotypes can be further differentiated into toxin variants, which are up to 99.9% identical in some cases. Mass spectrometric proteomic techniques have been established to differentiate the serotype or toxin variant of BoNT produced by varied strains of C. botulinum. Detection of potent biological toxins requires high analytical sensitivity and mass spectrometry based methods have been developed to determine the enzymatic activity of BoNT and the anthrax lethal toxins produced by B. anthracis. This enzymatic activity, unique for each toxin, is assessed with detection of the toxin-induced cleavage of strategically designed peptide substrates by MALDI-TOF mass spectrometry offering unparalleled specificity. Furthermore, activity assays allow for the assessment of the biological activity of a toxin and its potential health risk. Such methods have become important diagnostics for botulism and anthrax. Here, we review mass spectrometry based methods for the enzymatic activity of BoNT and the anthrax lethal factor toxin.

  9. Mass Spectrometric Analysis of Histone Proteoforms

    Science.gov (United States)

    Yuan, Zuo-Fei; Arnaudo, Anna M.; Garcia, Benjamin A.

    2014-06-01

    Histones play important roles in chromatin, in the forms of various posttranslational modifications (PTMs) and sequence variants, which are called histone proteoforms. Investigating modifications and variants is an ongoing challenge. Previous methods are based on antibodies, and because they usually detect only one modification at a time, they are not suitable for studying the various combinations of modifications on histones. Fortunately, mass spectrometry (MS) has emerged as a high-throughput technology for histone analysis and does not require prior knowledge about any modifications. From the data generated by mass spectrometers, both identification and quantification of modifications, as well as variants, can be obtained easily. On the basis of this information, the functions of histones in various cellular contexts can be revealed. Therefore, MS continues to play an important role in the study of histone proteoforms. In this review, we discuss the analysis strategies of MS, their applications on histones, and some key remaining challenges.

  10. High-Performance Liquid Chromatographic-Tandem Mass Spectrometric Determination of Itraconazole in Human Plasma for Bioavailability and Bioequivalence Studies

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Young Wook; Nam, Dae Young; Kang, Kyoung Hoon; Ha, Kyung Wook; Han, In Hee; Chang, Byung Kon; Yoon, Mi Kyeong; Lee, Jae Hwi [Chung-Ang University, Seoul (Korea, Republic of)

    2006-02-15

    A highly sensitive high-performance liquid chromatographic-tandem mass spectrometric method (HPLC-MSMS) has been developed to quantify itraconazole in human plasma for the purpose of pharmacokinetic studies. Sample preparation was carried out by liquid-liquid extraction using loratadine as an internal standard. Chromatographic separation used a YMC C{sub 18} column, giving an extremely fast total run time of 3 min. The method was validated and used for the bioequivalence study of itraconazole tablets in healthy male volunteers (n = 31). The lower limit of detection proved to be 0.2 ng /mL for itraconazole.

  11. Quantum dots assisted laser desorption/ionization mass spectrometric detection of carbohydrates: qualitative and quantitative analysis.

    Science.gov (United States)

    Bibi, Aisha; Ju, Huangxian

    2016-04-01

    A quantum dots (QDs) assisted laser desorption/ionization mass spectrometric (QDA-LDI-MS) strategy was proposed for qualitative and quantitative analysis of a series of carbohydrates. The adsorption of carbohydrates on the modified surface of different QDs as the matrices depended mainly on the formation of hydrogen bonding, which led to higher MS intensity than those with conventional organic matrix. The effects of QDs concentration and sample preparation method were explored for improving the selective ionization process and the detection sensitivity. The proposed approach offered a new dimension to the application of QDs as matrices for MALDI-MS research of carbohydrates. It could be used for quantitative measurement of glucose concentration in human serum with good performance. The QDs served as a matrix showed the advantages of low background, higher sensitivity, convenient sample preparation and excellent stability under vacuum. The QDs assisted LDI-MS approach has promising application to the analysis of carbohydrates in complex biological samples.

  12. Considerations for quantification of lipids in nerve tissue using MALDI mass spectrometric imaging

    Science.gov (United States)

    Landgraf, Rachelle R.; Garrett, Timothy J.; Prieto Conaway, Maria C.; Calcutt, Nigel A.; Stacpoole, Peter W.; Yost, Richard A.

    2013-01-01

    MALDI mass spectrometric imaging is a technique that provides the ability to identify and characterize endogenous and exogenous compounds spatially within tissue with relatively little sample preparation. While it is a proven methodology for qualitative analysis, little has been reported for its utility in quantitative measurements. In the current work, inherent challenges in MALDI quantification are addressed. Signal response is monitored over successive analyses of a single tissue section to minimize error due to variability in the laser, matrix application, and sample inhomogeneity. Methods for the application of an internal standard to tissue sections are evaluated and used to quantify endogenous lipids in nerve tissue. A precision of 5% or less standard error was achieved, illustrating that MALDI imaging offers a reliable means of in situ quantification for microgram-sized samples and requires minimal sample preparation. PMID:21953974

  13. Liquid chromatography-mass spectrometric determination of losartan and its active metabolite on dried blood spots.

    Science.gov (United States)

    Rao, R Nageswara; Raju, S Satyanarayana; Vali, R Mastan; Sankar, G Girija

    2012-08-01

    A simple and rapid quantitative bioanalytical liquid chromatography-tandem mass spectrometric (LC-MS/MS) method for simultaneous determination of losartan and its active metabolite, losartan carboxylic acid on rat dried blood spots was developed and validated as per regulatory guidelines. Losartan and its metabolite were extracted from dried blood spots using 50% aqueous methanol and separated on Waters XTerra(®) RP18 (250 mm × 4.6 mm, 5 μm) column using mobile phase composed of 40% acetonitrile and 60% aqueous ammonium acetate (10mM). The eluents were monitored using ESI tandem mass spectrometric detection with negative polarity in MRM mode using ion transitions m/z 421.2→179.0, m/z 435.3→157.0 and m/z 427.3→193.0 for losartan, losartan carboxylic acid and Irbesartan (internal standard), respectively. The method was validated over the linear range of 1-200 ng/mL and 5-1000 ng/mL with lower limits of quantification of 1.0 ng/mL and 5.0 ng/mL for losartan and losartan carboxylic acid, respectively. Inter and intra-day precision and accuracy (Bias) were below 5.96% and between -2.8 and 1.5%, respectively. The mean recoveries of the analytes from dried blood spots were between 89% and 97%. No significant carry over and matrix effects were observed. The stability of stock solution, whole blood, dried blood spot and processed samples were tested under different conditions and the results were found to be well within the acceptable limits. Additional validation parameters such as influence of hematocrit and spot volume were also evaluated and found to be well within the acceptable limits.

  14. [Application of PCA to diesel engine oil spectrometric analysis].

    Science.gov (United States)

    Liu, Tao; Tian, Hong-Xiang; Guo, Wen-Yong

    2010-03-01

    In order to study wear characteristics of a 6-cylinder diesel engine, six different working statuses were arranged by altering the clearance between cylinder and piston. Sixty-nine oil samples were taken from engine at different loads under 6 working statuses and analyzed by Spectroil M Instrument made in US. Principal component analysis (PCA) was applied to analyzing spectrometric data of sixty-nine oil samples and clustering those data according to elements and oil samples separately based on the weighted coefficient and principal component scores. All 21 elements were used in element clustering and only 6 wear-related elements, namely iron, chromium, aluminum, copper, plumbum and silicon, were used in sample clustering. It is shown that PCA effectively clustered oil spectrometric data into three different principal components according to elements. The projection of two different principal components exhibited five types of elements combinations, namely wear elements (Fe, Cr, Cu, Al and Pb), high concentration additives elements (Na, Zn, P, Ca and Mg), low concentration additives elements (Ba and B), base constituent of lubricating oils (C and H) and interferential elements (Ni, Ti, Mo, V, Ag and Sn). Furthermore, PCA clearly clustered oil samples according to different clearance between cylinder and piston in the diesel engine. The study suggests that analyzing oil spectrographic data by PCA could find the sources of different elements, monitor engine conditions and diagnose wear faults.

  15. Mass spectrometric composition and structural studies of petroleum sulfonates and petroleum sulfonate components for utilization in tertiary petroleum production

    Energy Technology Data Exchange (ETDEWEB)

    Belafi, L.; Decsy, Z.; Kerenyi, E.; Lukacs, J.

    1984-01-01

    A separation and mass spectrometric analytical method was developed for the separation and characterization of the monosulfonate fractions of petroleum sulfonate products. The technique is based on distillation and preparative column and thin-layer chromatography. The structure and carbon number distributions of monosulfonate fractions transformed to metilesters were measured based on their low resolution molecular mass spectra. The conditions of an actual petroleum container were simulated and the measurement of the effluent composition during its discharge revealed no change in the composition of monosulfonates.

  16. Carbon nanotubes as solid-phase extraction sorbents prior to atomic spectrometric determination of metal species: A review

    Energy Technology Data Exchange (ETDEWEB)

    Herrero Latorre, C., E-mail: carlos.herrero@usc.es [Universidad de Santiago de Compostela, Dpto. Quimica Analitica, Nutricion y Bromatologia, Facultad de Ciencias, Alfonso X el Sabio s/n, 27002 Lugo (Spain); Alvarez Mendez, J.; Barciela Garcia, J.; Garcia Martin, S.; Pena Crecente, R.M. [Universidad de Santiago de Compostela, Dpto. Quimica Analitica, Nutricion y Bromatologia, Facultad de Ciencias, Alfonso X el Sabio s/n, 27002 Lugo (Spain)

    2012-10-24

    Highlights: Black-Right-Pointing-Pointer The use of CNTs as sorbent for metal species in solid phase extraction has been described. Black-Right-Pointing-Pointer Physical and chemical strategies for functionalization of carbon nanotubes have been discussed. Black-Right-Pointing-Pointer Published analytical methods concerning solid phase extraction and atomic spectrometric determination have been reviewed. - Abstract: New materials have significant impact on the development of new methods and instrumentation for chemical analysis. From the discovery of carbon nanotubes in 1991, single and multi-walled carbon nanotubes - due to their high adsorption and desorption capacities - have been employed as sorption substrates in solid-phase extraction for the preconcentration of metal species from diverse matrices. Looking for successive improvements in sensitivity and selectivity, in the past few years, carbon nanotubes have been utilized as sorbents for solid phase extraction in three different ways: like as-grown, oxidized and functionalized nanotubes. In the present paper, an overview of the recent trends in the use of carbon nanotubes for solid phase extraction of metal species in environmental, biological and food samples is presented. The determination procedures involved the adsorption of metals on the nanotube surface, their quantitative desorption and subsequent measurement by means of atomic spectrometric techniques such as flame atomic absorption spectrometry, electrothermal atomic absorption spectrometry or inductively coupled plasma atomic emission spectrometry/mass spectrometry, among others. Synthesis, purification and types of carbon nanotubes, as well as the diverse chemical and physical strategies for their functionalization are described. Based on 140 references, the performance and general properties of the applications of solid phase extraction based on carbon nanotubes for metal species atomic spectrometric determination are discussed.

  17. Speciation analysis by gas chromatography with plasma source spectrometric detection

    Science.gov (United States)

    Łobiński, Ryszard; Adams, Freddy C.

    State-of-the-art species-selective analysis by gas chromatography (GC) with plasma source spectrometric detection is discussed for organometal and organometalloid compounds. Various plasmas, inductively coupled plasma, microwave induced plasma, capacitatively coupled plasma, direct current plasma and alternating current plasma, are characterized and critically compared as sources of radiation for atomic emission spectrometry and sources of ions for mass spectrometry. Interfaces between gas chromatography (packed, wide-bore, capillary and multicapillary) and plasma source spectrometry are characterized. Particular emphasis is given to applications of GC with plasma source detection to real-world analytical problems, which are comprehensively reviewed. The use of plasmas for the acquisition of auxiliary molecular information such as empirical formulae and structural information is discussed. Recent developments relating to sample preparation and presentation to the hyphenated system are addressed. The most significant trends in speciation analysis are highlighted.

  18. Mass spectrometric determination of early and advanced glycation in biology.

    Science.gov (United States)

    Rabbani, Naila; Ashour, Amal; Thornalley, Paul J

    2016-08-01

    Protein glycation in biological systems occurs predominantly on lysine, arginine and N-terminal residues of proteins. Major quantitative glycation adducts are found at mean extents of modification of 1-5 mol percent of proteins. These are glucose-derived fructosamine on lysine and N-terminal residues of proteins, methylglyoxal-derived hydroimidazolone on arginine residues and N(ε)-carboxymethyl-lysine residues mainly formed by the oxidative degradation of fructosamine. Total glycation adducts of different types are quantified by stable isotopic dilution analysis liquid chromatography-tandem mass spectrometry (LC-MS/MS) in multiple reaction monitoring mode. Metabolism of glycated proteins is followed by LC-MS/MS of glycation free adducts as minor components of the amino acid metabolome. Glycated proteins and sites of modification within them - amino acid residues modified by the glycating agent moiety - are identified and quantified by label-free and stable isotope labelling with amino acids in cell culture (SILAC) high resolution mass spectrometry. Sites of glycation by glucose and methylglyoxal in selected proteins are listed. Key issues in applying proteomics techniques to analysis of glycated proteins are: (i) avoiding compromise of analysis by formation, loss and relocation of glycation adducts in pre-analytic processing; (ii) specificity of immunoaffinity enrichment procedures, (iii) maximizing protein sequence coverage in mass spectrometric analysis for detection of glycation sites, and (iv) development of bioinformatics tools for prediction of protein glycation sites. Protein glycation studies have important applications in biology, ageing and translational medicine - particularly on studies of obesity, diabetes, cardiovascular disease, renal failure, neurological disorders and cancer. Mass spectrometric analysis of glycated proteins has yet to find widespread use clinically. Future use in health screening, disease diagnosis and therapeutic monitoring, and

  19. Determination of major phenolic acids, phenolic diterpenes and triterpenes in Rosemary (Rosmarinus Officinalis L.) by gas chromatography and mass spectrometry:

    OpenAIRE

    Vončina, Ernest; Doleček, Valter; Islamčević Razboršek, Maša; Brodnjak-Vončina, Darinka

    2007-01-01

    A gas chromatographic-mass spectrometric (GC-MS) method for the simultaneous identification and quantification of seven major phenolic and terpenic compounds in Rosmarinus officinalis L. was developed. The compounds were identified as trimethylsilyl (TMS) derivatives of phenolic acids (caffeic and rosmarinic acid), phenolic diterpene (carnosic acid), and pentacyclic triterpenes (ursolic, oleanolic, betulinic acid and betulin). These compounds have been identified by retention time and compari...

  20. Analysis of endocrine disrupting pesticides by capillary GC with mass spectrometric detection.

    Science.gov (United States)

    Matisová, Eva; Hrouzková, Svetlana

    2012-09-01

    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.

  1. Analysis of Endocrine Disrupting Pesticides by Capillary GC with Mass Spectrometric Detection

    Directory of Open Access Journals (Sweden)

    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.

  2. Evaluation of affinity-based serum clean-up in mass spectrometric analysis: Plastic vs monoclonal antibodies.

    Science.gov (United States)

    Rossetti, Cecilia; Levernæs, Maren C S; Reubsaet, Léon; Halvorsen, Trine G

    2016-11-04

    Mass spectrometric assays are now of great relevance for trace compound analysis in complex matrices such as serum and plasma samples. Especially in the quantification of low abundant protein-biomarkers, the choice of the sample preparation is crucial. In the present paper immunocapture and Molecular Imprinted Polymers (MIPs) have been applied in the determination of pro-gastrin-releasing peptide, a Small Cell Lung Cancer marker. These affinity-based techniques were compared in terms of matrix effect, limits of detection, repeatability and extraction specificity. In addition, protein precipitation was included for comparison as it is a typical sample preparation method of biological matrices. The results highlighted differences in the methods' performance and specificity, strongly affecting the outcome of the mass spectrometric determination. Plastic and monoclonal antibodies confirmed to be sensitive and specific sample preparations able to determine ProGRP at clinical relevant concentration, although only the use of monoclonal antibodies allowed the reliable quantification of ProGRP at reference levels (8pM). In addition better insight in the specificity of the three sample preparation techniques was gained. This might also be of interest for other biological applications.

  3. Review of procedures involving separation and preconcentration for the determination of cadmium using spectrometric techniques

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Sergio L.C. [Instituto de Quimica, Campus Universitario Ondina, Universidade Federal da Bahia, Salvador, Bahia 40170-290 (Brazil)]. E-mail: slcf@ufba.br; Andrade, Jailson B. de [Instituto de Quimica, Campus Universitario Ondina, Universidade Federal da Bahia, Salvador, Bahia 40170-290 (Brazil); Korn, Maria das Gracas A. [Instituto de Quimica, Campus Universitario Ondina, Universidade Federal da Bahia, Salvador, Bahia 40170-290 (Brazil); Pereira, Madson de G. [Departamento de Ciencias Exatas e da Terra Campus 1-Cabula, Universidade do Estado da Bahia, Salvador, Bahia 41195-001 (Brazil); Lemos, Valfredo A. [Laboratorio de Quimica Analitica, Campus de Jequie, Universidade Estadual do Sudoeste da Bahia, Jequie, Bahia 45200-190 (Brazil); Santos, Walter N.L. dos [Departamento de Ciencias Exatas e da Terra Campus 1-Cabula, Universidade do Estado da Bahia, Salvador, Bahia 41195-001 (Brazil); Rodrigues, Frederico de Medeiros [Instituto de Quimica, Campus Universitario Ondina, Universidade Federal da Bahia, Salvador, Bahia 40170-290 (Brazil); Empresa Baiana de Desenvolvimento Agricola S.A., Avenida Dorival Caymmi 15649, Itapoan, Salvador, Bahia 41635-150 (Brazil); Souza, Anderson S. [Instituto de Quimica, Campus Universitario Ondina, Universidade Federal da Bahia, Salvador, Bahia 40170-290 (Brazil); Instituto Multidisciplinar em Saude, Campus AnisioTeixeira, Universidade Federal da Bahia, Vitoria da Conquista, Bahia 45055-090 (Brazil); Ferreira, Hadla S. [Instituto de Quimica, Campus Universitario Ondina, Universidade Federal da Bahia, Salvador, Bahia 40170-290 (Brazil); Silva, Erik G.P. da [Instituto de Quimica, Campus Universitario Ondina, Universidade Federal da Bahia, Salvador, Bahia 40170-290 (Brazil)

    2007-07-16

    Spectrometric techniques for the analysis of trace cadmium have developed rapidly due to the increasing need for accurate measurements at extremely low levels of this element in diverse matrices. This review covers separation and preconcentration procedures, such as electrochemical deposition, precipitation, coprecipitation, solid phase extraction, liquid-liquid extraction (LLE) and cloud point extraction (CPE), and consider the features of the their application with several spectrometric techniques.

  4. Mass spectrometric analysis of O-linked oligosaccharides from various recombinant expression systems.

    Science.gov (United States)

    Kenny, Diarmuid T; Gaunitz, Stefan; Hayes, Catherine A; Gustafsson, Anki; Sjöblom, Magnus; Holgersson, Jan; Karlsson, Niclas G

    2013-01-01

    Analysis of O-linked glycosylation is one of the main challenges during structural validation of recombinant glycoproteins. With methods available for N-linked glycosylation in regard to oligosaccharide analysis as well as glycopeptide mapping, there are still challenges for O-linked glycan analysis. Here, we present mass spectrometric methodology for O-linked oligosaccharides released by reductive β-elimination. Using LC-MS and LC-MS(2) with graphitized carbon columns, oligosaccharides are analyzed without derivatization. This approach provides a high-throughput method for screening during clonal selection, as well as product structure verification, without impairing sequencing ability. The protocols are exemplified by analysis of glycoproteins from mammalian cell cultures (CHO cells) as well as insect cells and yeast. The data shows that the method can be successfully applied to both neutral and acidic O-linked oligosaccharides, where sialic acid, hexuronic acid, and sulfate are common substituents. Further characterization of O-glycans can be achieved using permethylation. Permethylation of O-linked oligosaccharides followed by direct infusion into the mass spectrometer provide information about oligosaccharide composition, and subsequent MS (n) experiments can be carried out to elucidate oligosaccharide structure including linkage information and sequence.

  5. Lipopeptides from the Banyan Endophyte, Bacillus subtilis K1: Mass Spectrometric Characterization of a Library of Fengycins

    Science.gov (United States)

    Pathak, Khyati V.; Keharia, Haresh; Gupta, Kallol; Thakur, Suman S.; Balaram, Padmanabhan

    2012-10-01

    Mass spectrometric analysis of a banyan endophyte, Bacillus subtilis K1, extract showing broad spectrum antifungal activity revealed a complex mixture of lipopeptides, iturins, surfactins, and fengycins. Fractionation by reversed-phase high performance liquid chromatography (HPLC) facilitated a detailed analysis of fengycin microheterogeneity. Matrix assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometric studies permitted the identification of several new fengycin variants. Four major sites of heterogeneity are identified: (1) N-terminus β-hydroxy fatty acid moiety, where chain length variation and the presence of unsaturation occur, (2) position 6 (Ala/Val/Ile/Leu), (3) position 10 (Val/Ile) within the macrocyclic ring, and (4) Gln to Glu replacement at position 8, resulting in fengycin variants that differ in mass by 1 Da. Diagnostic fragment ions provide a quick method for localizing the sites of variation in the macrocycle or the linear segment. Subsequent establishment of the sequences is achieved by MS/MS analysis of linear fengycin species produced by hydrolysis of the macrocyclic lactone. Unsaturation in the fatty acid chain and the presence of linear precursors in the B. subtilis K1 extract are also established by mass spectrometry. The anomalous distribution of intensities within isotopic multiplets is a diagnostic for Gln/Glu replacements. High resolution mass spectrometry facilitates the identification of fengycin species differing by 1 Da by localizing the variable position (Gln8/Glu8) in the fengycin variants.

  6. Status of mass spectrometric radiocarbon detection at ETHZ

    Energy Technology Data Exchange (ETDEWEB)

    Seiler, Martin; Maxeiner, Sascha; Wacker, Lukas; Synal, Hans-Arno

    2015-10-15

    A prototype of a mass spectrometric radiocarbon detection instrument without accelerator stage was built for the first time and set into operation at ETH Zurich. The system is designed as an experimental platform to optimize performance of {sup 14}C detection at low ion energies and to study the most relevant processes that may limit system performance. The optimized stripper unit incorporates differential pumping to maintain a low gas outflow and a revised tube design to better match the phase space volume of the ion beam at low energies. The system is fully operational and has demonstrated true radiocarbon dating capabilities. The overall beam transmission through the stripper tube is about 40% for the 1{sup +} charge state. Radiocarbon analyses with an overall precision of 0.6% were obtained on a single sample under regular measurement conditions. By analyzing multiple targets of the same sample material an uncertainty level of 0.3% has been reached. The background level corresponds to a radiocarbon age of 40,000 years.

  7. Multisphere neutron spectrometric system with thermoluminescence dosemeters: sensitive improvement.

    Science.gov (United States)

    Gregori, B; Papadópulos, S; Cruzate, J; Kunst, J J

    2002-01-01

    In this work, a neutron spectrometric system based on a set of moderating spheres with thermoluminescence detectors (TLD) is presented. The system at the Nuclear Regulatory Authority (ARN) Dosimetry Laboratory consists of 12 solid spheres made of high-density polyethylene (p = 0.95 g x cm(-3)), with diameters ranging from 2" to 12" and TLD sensitive to thermal and gamma radiation, namely TLD-600 and TLD-700, located at the centre of the spheres. The neutron response matrix for this Bonner Sphere Spectrometer (BSS) was calculated using the MCNP-IVB code and the library ENDF/B-VI in the energy range between thermal neutrons and 100 MeV. The neutron spectrum was obtained using the LOUH182 unfolding code. The improvement in sensitivity of the system is based on the election of a different heating cycle of the TLD that allows an increase in sensitivity by a factor of 2.6 compared with the standard laboratory treatment. The system response for the calibration with an Am-Be source is presented.

  8. Mass spectrometric detection of proteins in non-aqueous media : the case of prion proteins in biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Douma, M.D.; Kerr, G.M.; Brown, R.S.; Keller, B.O.; Oleschuk, R.D. [Queen' s Univ., Kingston, ON (Canada). Dept. of Chemistry

    2008-08-15

    This paper presented a filtration method for detecting protein traces in non-aqueous media. The extraction technique used a mixture of acetonitrile, non-ionic detergent and water along with filter disks with embedded C{sub 8}-modified silica particles to capture the proteins from non-aqueous samples. The extraction process was then followed by an elution of the protein from the filter disk and direct mass spectrometric detection and tryptic digestion with peptide mapping and MS/MS fragmentation of protein-specific peptides. The method was used to detect prion proteins in spiked biodiesel samples. A tryptic peptide with the sequence YGQGSPGGNR was used for unambiguous identification. Results of the study showed that the method is suitable for the large-scale testing of protein impurities in tallow-based biodiesel production processes. 33 refs., 6 figs.

  9. Chromatographic and mass spectrometric techniques in studies on oxidative stress in autism.

    Science.gov (United States)

    Kałużna-Czaplińska, Joanna; Jóźwik-Pruska, Jagoda

    2016-04-15

    Healthy body is characterized by the presence of a dynamic and balanced equilibrium between the production of reactive oxygen species (ROS) and the antioxidant capacity. In oxidative stress this balance is switched to reactions of oxidation leading to increased production of ROS, exceeding the capacity of physiological antioxidant systems. Oxidative stress is known to be linked to many disturbances, disorders and diseases. One of these is the autism spectrum disorder (ASD). ASD is a neurodevelopmental disorder manifested by abnormalities in social communication and interaction, as well as by occurrence of repetitive, restricted patterns of behavior or activities. It is believed that adequate knowledge about the oxidative stress biomarkers and the possibility of their reliable measuring could be useful in broadening knowledge on various diseases including ASD. A high number of compounds have been proposed as biomarkers of oxidative stress. Some of these are connected with the severity of ASD. The present review gives a summary of the chromatographic techniques used for the determination of biomarkers for oxidative stress in autism, and of other compounds important in this context. The first part of the review focuses on the correlation between oxidative stress and autism. The second part describes applications of chromatographic and mass spectrometric methods to the analysis of different metabolites connected with oxidative stress in biological fluids of autistic children. Advantages as well as disadvantages of the application of these methods for the analysis of different types of oxidative stress biomarkers are discussed.

  10. Comprehensive ultra-performance liquid chromatographic separation and mass spectrometric analysis of eicosanoid metabolites in human samples.

    Science.gov (United States)

    Wang, Yan; Armando, Aaron M; Quehenberger, Oswald; Yan, Chao; Dennis, Edward A

    2014-09-12

    Over the past decade, the number of known eicosanoids has expanded immensely and we have now developed an ultra-performance liquid chromatography-electrospray ionization triple quadrupole mass spectrometric (UPLC-QTRAP/MS/MS) method to monitor and quantify numerous eicosanoids. The UPLC-QTRAP/MS/MS approach utilizes scheduled multiple reaction monitoring (MRM) to optimize sensitivity, number of metabolites that can be analyzed and the time requirement of the analysis. A total of 184 eicosanoids including 26 deuterated internal standards can be separated and monitored in a single 5min UPLC run. To demonstrate a practical application, human plasma samples were analyzed following solid-phase extraction (SPE) and the recovery rate and matrix effects were determined for the 26 deuterated internal standards added to the plasma. The method was validated and shown to be sensitive with the limit of quantitation at pg levels for most compounds, accurate with recovery rates of 70-120%, and precise with a CVeicosanoids.

  11. Direct tandem mass spectrometric analysis of amino acids in plasma using fluorous derivatization and monolithic solid-phase purification.

    Science.gov (United States)

    Tamashima, Erina; Hayama, Tadashi; Yoshida, Hideyuki; Imakyure, Osamu; Yamaguchi, Masatoshi; Nohta, Hitoshi

    2015-11-10

    In this study, we developed a novel direct tandem mass spectrometric method for rapid and accurate analysis of amino acids utilizing a fluorous derivatization and purification technique. Amino acids were perfluoroalkylated with 2H,2H,3H,3H-perfluoroundecan-1-al in the presence of 2-picoline borane via reductive amination. The derivatives were purified by perfluoroalkyl-modified silica-based monolithic solid-phase extraction (monolithic F-SPE), and directly analyzed by tandem mass spectrometry using electrospray ionization without liquid chromatographic separation. The perfluoroalkyl derivatives could be sufficiently distinguished from non-fluorous compounds, i.e. the biological matrix, due to their fluorous interaction. Thus, rapid and accurate determination of amino acids was accomplished. The method was validated with human plasma samples and applied to the analysis of amino acids in the plasma of mice with maple syrup urine disease or phenylketonuria.

  12. Ultrasound-assisted emulsification of cosmetic samples prior to elemental analysis by different atomic spectrometric techniques.

    Science.gov (United States)

    Lavilla, I; Cabaleiro, N; Costas, M; de la Calle, I; Bendicho, C

    2009-11-15

    In this work, ultrasound-assisted emulsification with a probe system is proposed as a rapid and simple sample treatment for atomic spectrometric determinations (Electrothermal Atomic Absorption Spectrometry, Inductively Coupled Plasma Optical Emission Spectrometry, Flame Atomic Absorption Spectrometry and Cold Vapour Atomic Absorption Spectrometry) of trace elements (As, Cd, Cr, Cu, Hg, Mg, Mn, Ni, Sr and Zn) in cosmetic samples such as shampoos, gel (hair gel), crèmes (body milk, hair conditioner) and oil (body oil). The type of dispersion medium, the sample mass-to-dispersion medium volume ratio, as well as the parameters related to the ultrasound-assisted emulsification (sonication amplitude and treatment time) were exhaustively studied. Only 1 min of ultrasonic shaking and a dispersion medium containing 0.5% (w/v) of SDS+3% (v/v) of HNO(3) or HCl allows obtaining a stable emulsion at least for 3 months. Thermal programs, nebulization of emulsions, speed of pumps and concentration of reagents used in cold vapour generation were optimized. Calibration using aqueous standards was feasible in all cases. Calibration by the standard addition method and recovery studies was also applied for validation. Microwave-assisted digestion and Inductively Coupled Plasma Mass Spectrometry were used for comparison purposes. Relative standard deviations from analysis of five independent emulsions were less than 9% in all cases.

  13. Mass spectrometric detection of short-lived drug metabolites generated in an electrochemical microfluidic chip.

    Science.gov (United States)

    van den Brink, Floris T G; Büter, Lars; Odijk, Mathieu; Olthuis, Wouter; Karst, Uwe; van den Berg, Albert

    2015-02-03

    The costs of drug development have been rising exponentially over the last six decades, making it essential to select drug candidates in the early drug discovery phases before proceeding to expensive clinical trials. Here, we present novel screening methods using an electrochemical chip coupled online to mass spectrometry (MS) or liquid chromatography (LC) and MS, to generate phase I and phase II drug metabolites and to demonstrate protein modification by reactive metabolites. The short transit time (∼4.5 s) between electrochemical oxidation and mass spectrometric detection, enabled by an integrated electrospray emitter, allows us to detect a short-lived radical metabolite of chlorpromazine which is too unstable to be detected using established test routines. In addition, a fast way to screen candidate drugs is established by recording real-time mass voltammograms, which allows one to identify the drug metabolites that are expected to be formed upon oxidation by applying a linear potential sweep and simultaneously detect oxidation products. Furthermore, detoxification of electrochemically generated reactive metabolites of paracetamol was mimicked by their adduct formation with the antioxidant glutathione. Finally, the potential toxicity of reactive metabolites can be investigated by the modification of proteins, which was demonstrated by modification of carbonic anhydrase I with electrochemically generated reactive metabolites of paracetamol. With this series of experiments, we demonstrate the potential of this electrochemical chip as a complementary tool for a variety of drug metabolism studies in the early stages of drug discovery.

  14. First experiment of spectrometric observation of hydroxyl emission and rotational temperature in the mesopause in China

    Institute of Scientific and Technical Information of China (English)

    ZHU YaJun; XU JiYao; YUAN Wei; LIU Xiao

    2012-01-01

    A SpectroMeter of Atmospheric RadiaTion (SMART) was developed and installed at the Xinglong station of the National Astronomical Observatories in Hebei province,China,which was supported by the Meridian Project [ 1].The experimental tests of spectrometric observation of the hydroxyl emission and rotational temperature in China were conducted for the first time on the night of February 23,2011 and the night of April 27,2011,respectively.OH 6-2 band and OH 8-3 band spectra were measured and the rotational temperature was retrieved.Hourly average temperatures (186.82+-6.40) K of OH 8-3 band and (178.07±6.73) K of OH 6-2 band were derived from the spectra observed on the night of February 23,2011.Intensities and rotational temperature against local time were determined by the spectra measured in the whole night of April 27,2011.The rotational temperature was consistent with the spatial average temperature of NRLMSISE00 empirical model at height 83-91 km and the average temperature of TIMED/SABER from April to May of seven years at height 83-91 km,with some discrepancies.The results showed that the new instrument and the retrieval method of the rotational temperature can give reasonable results of the airglow emission of OH and the temperature of mesopause.

  15. Mass spectrometric study of rhamnolipid biosurfactants and their interactions with cell membrane phospholipids

    Directory of Open Access Journals (Sweden)

    Pashynska V. A.

    2009-12-01

    Full Text Available Aim. To examine the formation of supramolecular complexes of biogenous rhamnolipids with membrane phospholipids that is considered as a molecular mechanism of the biosurfactants antimicrobial action. Method. In the present work rhamnolipid biosurfactant samples produced by Pseudomonas sp. PS-17 strain have been investigated by electrospray ionization mass spectrometry for the first time. Results. As a result of the study, characteristic mass spectra of the rhamnolipid samples were obtained, that can be used as reference spectra for mass spectrometric identification of the compounds in any biological or industrial samples. At the next stage of the experiments the pair systems, containing the biosurfactants and a membrane phospholipid dipalmitoylphosphatidylcholine, have been tested. The cationized noncovalent complexes of the rhamnolipids with the phospholipid were observed in the spectra. Conclusions. The results obtained testify to the consideration that rhamnolipids (similar to other membranotropic agents can form stable supramolecular complexes with membrane phospholipids that are able to evoke the biosurfactants antimicrobial action. A great potential of electrospray ionization mass spectrometry for the biosurfactants identification and study has been demonstrated in the work.

  16. Experimental characterization of the Clear-PEM scanner spectrometric performance

    Science.gov (United States)

    Bugalho, R.; Carriço, B.; Ferreira, C. S.; Frade, M.; Ferreira, M.; Moura, R.; Ortigão, C.; Pinheiro, J. F.; Rodrigues, P.; Rolo, I.; Silva, J. C.; Trindade, A.; Varela, J.

    2009-10-01

    In the framework of the Clear-PEM project for the construction of a high-resolution and high-specificity scanner for breast cancer imaging, a Positron Emission Mammography tomograph has been developed and installed at the Instituto Português de Oncologia do Porto hospital. The Clear-PEM scanner is mainly composed by two planar detector heads attached to a robotic arm, trigger/data acquisition electronics system and computing servers. The detector heads hold crystal matrices built from 2 × 2 × 20 mm3 LYSO:Ce crystals readout by Hamamatsu S8550 APD arrays. The APDs are optically coupled to both ends of the 6144 crystals in order to extract the DOI information for each detected event. Each one of 12288 APD's pixels is read and controlled by Application Specific Integrated Circuits water-cooled by an external cooling unit. The Clear-PEM frontend boards innovative design results in a unprecedented integration of the crystal matrices, APDs and ASICs, making Clear-PEM the PET scanner with the highest number of APD pixels ever integrated so far. In this paper, the scanner's main technical characteristics, calibration strategies and the first spectrometric performance evaluation in a clinical environment are presented. The first commissioning results show 99.7% active channels, which, after calibration, have inter-pixel and absolute gain distributions with dispersions of, respectively, 12.2% and 15.3%, demonstrating that despite the large number of channels, the system is uniform. The mean energy resolution at 511 keV is of 15.9%, with a 8.8% dispersion, and the mean CDOI-1 is 5.9%/mm, with a 7.8% dispersion. The coincidence time resolution, at 511 keV, for a energy window between 400 and 600 keV, is 5.2 ns FWHM.

  17. Oxidative Ionization Under Certain Negative-Ion Mass Spectrometric Conditions

    Science.gov (United States)

    Hassan, Isra; Pavlov, Julius; Errabelli, Ramu; Attygalle, Athula B.

    2017-02-01

    1,4-Hydroquinone and several other phenolic compounds generate (M - 2) -• radical-anions, rather than deprotonated molecules, under certain negative-ion mass spectrometric conditions. In fact, spectra generated under helium-plasma ionization (HePI) conditions from 1,4-hydroquinone and 1,4-benzoquinone (by electron capture) were practically indistinguishable. Because this process involves a net loss of H• and H+, it can be termed oxidative ionization. The superoxide radical-anion (O2 -•), known to be present in many atmospheric-pressure plasma ion sources operated in the negative mode, plays a critical role in the oxidative ionization process. The presence of a small peak at m/z 142 in the spectrum of 1,4-hydroquinone, but not in that of 1,4-benzoquinone, indicated that the initial step in the oxidative ionization process is the formation of an O2 -• adduct. On the other hand, under bona fide electrospray ionization (ESI) conditions, 1,4-hydroquinone generates predominantly an (M - 1) - ion. It is known that at sufficiently high capillary voltages, corona discharges begin to occur even in an ESI source. At lower ESI capillary voltages, deprotonation predominates; as the capillary voltage is raised, the abundance of O2 -• present in the plasma increases, and the source in turn increasingly behaves as a composite ESI/APCI source. While maintaining post-ionization ion activation to a minimum (to prevent fragmentation), and monitoring the relative intensities of the m/z 109 (due to deprotonation) and 108 (oxidative ionization) peaks recorded from 1,4-hydroquinone, a semiquantitative estimation of the APCI contribution to the overall ion-generation process can be obtained.

  18. Experimental characterization of the Clear-PEM scanner spectrometric performance

    Energy Technology Data Exchange (ETDEWEB)

    Bugalho, R; Carrico, B; Ferreira, C S; Frade, M; Ferreira, M; Moura, R; Ortigao, C; Pinheiro, J F; Rodrigues, P; Rolo, I; Silva, J C; Trindade, A; Varela, J [Laboratorio de Instrumentacao e Fisica Experimental de Particulas (LIP), Av. Elias Garcia 14-1, 1000-149 Lisboa (Portugal)], E-mail: frade@lip.pt

    2009-10-15

    In the framework of the Clear-PEM project for the construction of a high-resolution and high-specificity scanner for breast cancer imaging, a Positron Emission Mammography tomograph has been developed and installed at the Instituto Portugues de Oncologia do Porto hospital. The Clear-PEM scanner is mainly composed by two planar detector heads attached to a robotic arm, trigger/data acquisition electronics system and computing servers. The detector heads hold crystal matrices built from 2 x 2 x 20 mm{sup 3} LYSO:Ce crystals readout by Hamamatsu S8550 APD arrays. The APDs are optically coupled to both ends of the 6144 crystals in order to extract the DOI information for each detected event. Each one of 12288 APD's pixels is read and controlled by Application Specific Integrated Circuits water-cooled by an external cooling unit. The Clear-PEM frontend boards innovative design results in a unprecedented integration of the crystal matrices, APDs and ASICs, making Clear-PEM the PET scanner with the highest number of APD pixels ever integrated so far. In this paper, the scanner's main technical characteristics, calibration strategies and the first spectrometric performance evaluation in a clinical environment are presented. The first commissioning results show 99.7% active channels, which, after calibration, have inter-pixel and absolute gain distributions with dispersions of, respectively, 12.2% and 15.3%, demonstrating that despite the large number of channels, the system is uniform. The mean energy resolution at 511 keV is of 15.9%, with a 8.8% dispersion, and the mean C{sub DOI}{sup -1} is 5.9%/mm, with a 7.8% dispersion. The coincidence time resolution, at 511 keV, for a energy window between 400 and 600 keV, is 5.2 ns FWHM.

  19. Spectrometric and Voltammetric Analysis of Urease – Nickel Nanoelectrode as an Electrochemical Sensor

    Directory of Open Access Journals (Sweden)

    Rene Kizek

    2007-07-01

    Full Text Available Urease is the enzyme catalyzing the hydrolysis of urea into carbon dioxide andammonia. This enzyme is substrate-specific, which means that the enzyme catalyzes thehydrolysis of urea only. This feature is a basic diagnostic criterion used in thedetermination of many bacteria species. Most of the methods utilized for detection ofurease are based on analysis of its enzyme activity – the hydrolysis of urea. The aim of thiswork was to detect urease indirectly by spectrometric method and directly by voltammetricmethods. As spectrometric method we used is called indophenol assay. The sensitivity ofdetection itself is not sufficient to analyse the samples without pre-concentration steps.Therefore we utilized adsorptive transfer stripping technique coupled with differential pulse voltammetry to detect urease. The influence of accumulation time, pH of supporting electrolyte and concentration of urease on the enzyme peak height was investigated. Under the optimized experimental conditions (0.2 M acetate buffer pH 4.6 and accumulation time of 120 s the detection limit of urease evaluated as 3 S/N was 200 ng/ml. The activity of urease enzyme depends on the presence of nickel. Thus the influence of nickel(II ions on electrochemical response of the enzyme was studied. Based on the results obtained the interaction of nickel(II ions and urease can be determined using electrochemical methods. Therefore we prepared Ni nanoelectrodes to measure urease. The Ni nanoelectrodes was analysed after the template dissolution by scanning electron microscopy. The results shown vertically aligned Ni nanopillars almost covered the electrode surface, whereas the defect places are minor and insignificant in comparison with total electrode surface. We were able to not only detect urease itself but also to distinguish its native and denatured form.

  20. Chromatographic, Spectroscopic and Mass Spectrometric Approaches for Exploring the Habitability of Mars in 2012 and Beyond with the Curiosity Rover

    Science.gov (United States)

    Mahaffy, Paul

    2012-01-01

    The Sample Analysis at Mars (SAM) suite of instruments on the Curiosity Rover of Mars Science Laboratory Mission is designed to provide chemical and isotopic analysis of organic and inorganic volatiles for both atmospheric and solid samples. The goals of the science investigation enabled by the gas chromatograph mass spectrometer and tunable laser spectrometer instruments of SAM are to work together with the other MSL investigations is to quantitatively assess habitability through a series of chemical and geological measurements. We describe the multi-column gas chromatograph system employed on SAM and the approach to extraction and analysis of organic compounds that might be preserved in ancient martian rocks.

  1. Hydrogen--deuterium exchange in water vapor: the mass spectrometric sensitivities and the equilibrium constant

    Energy Technology Data Exchange (ETDEWEB)

    Pyper, J.W.; Dupzyk, R.J.; Friesen, R.D.; Bernasek, S.L.; May, C.A.; Echeverria, A.W.; Tolman, L.F.

    1976-04-21

    The equilibrium constant, K/sub HDO/, for the reaction H/sub 2/O + D/sub 2/O = 2HDO can be expressed as an intensity ratio, I, measured mass spectrometrically, times a sensitivity ratio, S, measured in mass spectrometric calibration experiments. The latter is difficult to measure and previously was assumed to be unity. The 2.4 percent discrepancy between K's from theoretical calculations and direct mass spectrometric measurements might be explained by another value of S. An indirect measurement of S using a pulsed-molecular beam quadrupole mass filter that has a unique three-chamber, three-leak gas inlet system is reported. The results show the sensitivities are probably equal and therefore S = 1. Systematic errors were found in the procedure, however, which precluded an unambiguous test of the theory.

  2. Low-activity spectrometric gamma-ray logging technique for delineation of coal/rock interfaces in dry blast holes.

    Science.gov (United States)

    Asfahani, J; Borsaru, M

    2007-06-01

    A low-activity spectrometric gamma-ray logging technique is proposed in this paper as a sensitive tool for the delineation of coal/rock interfaces in dry blast holes. The advantages and superiority of this technique over traditional micro-density non-spectrometric gamma-ray tools are demonstrated.

  3. Protein nitration in biological aging: proteomic and tandem mass spectrometric characterization of nitrated sites.

    Science.gov (United States)

    Kanski, Jaroslaw; Schöneich, Christian

    2005-01-01

    Proteomic techniques for the identification of 3-nitrotyrosine-containing proteins in various biological systems are described with emphasis on the direct mass spectrometric detection and sequencing of 3-nitrotyrosine-containing peptides. Strengths and weaknesses of various separation and mass spectrometric techniques are discussed. Some examples for the MS/MS analysis of nitrated peptides obtained from aging rat heart and skeletal muscle are provided, such as nitration of Tyr105 of the mitochondrial electron-transfer flavoprotein and Tyr14 of creatine kinase.

  4. Considerations for quantification of lipids in nerve tissue using matrix-assisted laser desorption/ionization mass spectrometric imaging.

    Science.gov (United States)

    Landgraf, Rachelle R; Garrett, Timothy J; Conaway, Maria C Prieto; Calcutt, Nigel A; Stacpoole, Peter W; Yost, Richard A

    2011-10-30

    Matrix-assisted laser desorption/ionization (MALDI) mass spectrometric imaging is a technique that provides the ability to identify and characterize endogenous and exogenous compounds spatially within tissue with relatively little sample preparation. While it is a proven methodology for qualitative analysis, little has been reported for its utility in quantitative measurements. In the current work, inherent challenges in MALDI quantification are addressed. Signal response is monitored over successive analyses of a single tissue section to minimize error due to variability in the laser, matrix application, and sample inhomogeneity. Methods for the application of an internal standard to tissue sections are evaluated and used to quantify endogenous lipids in nerve tissue. A precision of 5% or less standard error was achieved, illustrating that MALDI imaging offers a reliable means of in situ quantification for microgram-sized samples and requires minimal sample preparation.

  5. Quantitative MALDI tandem mass spectrometric imaging of cocaine from brain tissue with a deuterated internal standard.

    NARCIS (Netherlands)

    Pirman, D.A.; Reich, R.F.; Kiss, A.; Heeren, R.M.A.; Yost, R.A.

    2013-01-01

    Mass spectrometric imaging (MSI) is an analytical technique used to determine the distribution of individual analytes within a given sample. A wide array of analytes and samples can be investigated by MSI, including drug distribution in rats, lipid analysis from brain tissue, protein differentiation

  6. Terverticillate Penicillia studied by direct electrospray mass spectrometric profiling of crude extracts: I. Chemosystematics

    DEFF Research Database (Denmark)

    Smedsgaard, Jørn; Frisvad, Jens Christian

    1997-01-01

    A chemosystematic study of 339 isolates from all known terverticillate Penicillium taxa was performed using electrospray mass spectrometric analysis of extractable metabolites. The mass profiles were made by injecting crude plug extracts made from cultures grown on Czapek Yeast Autolysate agar (C...... to known secondary metabolites were, however, found in all mass profiles. (C) 1997 Elsevier Science Ltd....

  7. Retrospective detection of exposure to organophosphorus anti-cholinesterases: Mass spectrometric analysis of phosphylated human butyrylcholinesterase

    NARCIS (Netherlands)

    Fidder, A.; Hulst, A.G.; Noort, D.; Ruiter, R. de; Schans, M.J. van der; Benschop, H.P.; Langenberg, J.P.

    2002-01-01

    In this paper a novel and general procedure is presented for detection of organophosphate-inhibited human butyrylcholinesterase (HuBuChE), which is based on electrospray tandem mass spectrometric analysis of phosphylated nonapeptides obtained after pepsin digestion of the enzyme. The utility of this

  8. QuEChERS: um método moderno de preparo de amostra para determinação multirresíduo de pesticidas em alimentos por métodos cromatográficos acoplados à espectrometria de massas QuEChERS: a modern sample preparation method for pesticide multiresidue determination in food by chromatographic methods coupled to mass spectrometry

    Directory of Open Access Journals (Sweden)

    Osmar D. Prestes

    2009-01-01

    Full Text Available This review attempts to provide an updated overview of the Quick, Easy, Cheap, Effective, Ruged and Safe (QuEChERS multiresidue extraction method, that involves initial extraction in acetonitrile, an extraction/partition step after the addition of salt, and a cleanup step utilizing dispersive solid phase extraction. QuEChERS method is nowadays the most applied extraction method for the determination of pesticide residues in food samples, providing acceptable recoveries for acidic, neutral and basic pesticides. Several applications for various food matrices (fruits, vegetables, cereals and others in combination with chromatographic mass spectrometry analysis were presented.

  9. Method of Gas Filled Time of Flight in AMS Measurement

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Isobaric interference is the main problem to be overcome in determination the long-livedradioisotopes. Energy loss method was used to measurement of these nuclides, but in the low energyaccelerator, the △E-E method is limited. In order to improve the power of isobaric identification in theaccelerator mass spectrometric measurements, a gas-filled time-of-flight (GF-TOF) spectrometric detectorhas been designed and set up.

  10. Mass spectrometric analysis of electrophoretically separated allergens and proteases in grass pollen diffusates

    Directory of Open Access Journals (Sweden)

    Geczy Carolyn L

    2003-09-01

    Full Text Available Abstract Background Pollens are important triggers for allergic asthma and seasonal rhinitis, and proteases released by major allergenic pollens can injure airway epithelial cells in vitro. Disruption of mucosal epithelial integrity by proteases released by inhaled pollens could promote allergic sensitisation. Methods Pollen diffusates from Kentucky blue grass (Poa pratensis, rye grass (Lolium perenne and Bermuda grass (Cynodon dactylon were assessed for peptidase activity using a fluorogenic substrate, as well as by gelatin zymography. Following one- or two-dimensional gel electrophoresis, Coomassie-stained individual bands/spots were excised, subjected to tryptic digestion and analysed by mass spectrometry, either MALDI reflectron TOF or microcapillary liquid chromatography MS-MS. Database searches were used to identify allergens and other plant proteins in pollen diffusates. Results All pollen diffusates tested exhibited peptidase activity. Gelatin zymography revealed high Mr proteolytic activity at ~ 95,000 in all diffusates and additional proteolytic bands in rye and Bermuda grass diffusates, which appeared to be serine proteases on the basis of inhibition studies. A proteolytic band at Mr ~ 35,000 in Bermuda grass diffusate, which corresponded to an intense band detected by Western blotting using a monoclonal antibody to the timothy grass (Phleum pratense group 1 allergen Phl p 1, was identified by mass spectrometric analysis as the group 1 allergen Cyn d 1. Two-dimensional analysis similarly demonstrated proteolytic activity corresponding to protein spots identified as Cyn d 1. Conclusion One- and two-dimensional electrophoretic separation, combined with analysis by mass spectrometry, is useful for rapid determination of the identities of pollen proteins. A component of the proteolytic activity in Bermuda grass diffusate is likely to be related to the allergen Cyn d 1.

  11. Characterizations of the radioactive waste by the remotely-controlled collimated spectrometric system

    Energy Technology Data Exchange (ETDEWEB)

    Stepanov, Vyacheslav E.; Potapov, Victor N.; Smirnov, Sergey V.; Ivanov, Oleg P. [National Research Centre Kurchatov Institute, Moscow, (Russian Federation)

    2015-07-01

    Decontamination and decommissioning of the research reactors MR (Testing Reactor) and RFT (Reactor of Physics and Technology) has recently been initiated in the National Research Center (NRC) 'Kurchatov institute', Moscow. In the building, neighboring to the reactor, the storage of HLRW is located. The storage is made of monolithic concrete in which steel cells depth 4 m are located. In cells of storage the HLRW packed into cases are placed. These the radioactive waste are also subject to export on long storage in the specialized organization. For characterization of the radioactive waste in cases the remote-controlled collimated spectrometer system was used. The system consists of a spectrometric collimated gamma-ray detector, a color video camera and a control unit, mounted on a rotator, which are mounted on a tripod with the host computer. For determination of specific activity of radionuclides in cases, it is developed programs of calculation of coefficients of proportionality of specific activity to the corresponding speeds of the account in peaks of full absorption at single specific activity of radionuclides in cases. For determination of these coefficients the mathematical model of spectrometer system based on the Monte-Carlo method was used. Dependences of calibration coefficients for various radionuclides from distance between the detector and a case at various values of the radioactive waste density in cases are given. Measurements of specific activity in cases are taken and are discussed. By results of measurements decisions on the appeal of the radioactive waste being in cases are made. (authors)

  12. Assessment of predictive indices for glioblastomas radiation therapy: comparison of perfusion MRI and spectrometric imagery by magnetic resonance; Evaluation d'indices predictifs pour la radiotherapie des glioblastomes: comparaison de l'IRM de perfusion et de l'imagerie de spectrometrie par resonance magnetique

    Energy Technology Data Exchange (ETDEWEB)

    Lemoine, J.M.; Laprie, A.; Moyal Cohen-Jonathan, E.; Ken, S. [Departement de radiotherapie, institut Claudius-Regaud, 31 - Toulouse (France); Lemoine, J.M.; Laprie, A.; Franceries, X.; Lotterie, J.A.; Celsis, P.; Lubrano, V.; Berry, I.; Ken, S. [Inserm, UMR 825, imagerie cerebrale et handicaps neurologiques, 31 - Toulouse (France); Lemoine, J.M.; Franceries, X. [Universite Paul-Sabatier, 31 - Toulouse (France); Lotterie, J.A.; Berry, I. [Departement de biophysique, CHU Rangueil, 31 - Toulouse (France); Lubrano, V. [Departement de neurochirurgie, CHU Rangueil, 31 - Toulouse (France)

    2010-10-15

    The authors report the comparison of several imagery modalities: anatomic imagery (T1-weighted MRI after gadolinium injection and T2-weighted MRI), metabolic imagery (spectrometric imagery by magnetic resonance) and functional imagery (perfusion MRI). This comparison has been performed within the frame of a prospective clinic test associating a radiosensitizer concomitant with a radiation therapy of glioblastomas. It appears that the integration of data of spectrometric imagery by magnetic resonance and of perfusion MRI is a promising method to overcome the resistance of glioblastomas. Short communication

  13. iMS2Flux – a high–throughput processing tool for stable isotope labeled mass spectrometric data used for metabolic flux analysis

    Directory of Open Access Journals (Sweden)

    Poskar C Hart

    2012-11-01

    Full Text Available Abstract Background Metabolic flux analysis has become an established method in systems biology and functional genomics. The most common approach for determining intracellular metabolic fluxes is to utilize mass spectrometry in combination with stable isotope labeling experiments. However, before the mass spectrometric data can be used it has to be corrected for biases caused by naturally occurring stable isotopes, by the analytical technique(s employed, or by the biological sample itself. Finally the MS data and the labeling information it contains have to be assembled into a data format usable by flux analysis software (of which several dedicated packages exist. Currently the processing of mass spectrometric data is time-consuming and error-prone requiring peak by peak cut-and-paste analysis and manual curation. In order to facilitate high-throughput metabolic flux analysis, the automation of multiple steps in the analytical workflow is necessary. Results Here we describe iMS2Flux, software developed to automate, standardize and connect the data flow between mass spectrometric measurements and flux analysis programs. This tool streamlines the transfer of data from extraction via correction tools to 13C-Flux software by processing MS data from stable isotope labeling experiments. It allows the correction of large and heterogeneous MS datasets for the presence of naturally occurring stable isotopes, initial biomass and several mass spectrometry effects. Before and after data correction, several checks can be performed to ensure accurate data. The corrected data may be returned in a variety of formats including those used by metabolic flux analysis software such as 13CFLUX, OpenFLUX and 13CFLUX2. Conclusion iMS2Flux is a versatile, easy to use tool for the automated processing of mass spectrometric data containing isotope labeling information. It represents the core framework for a standardized workflow and data processing. Due to its flexibility

  14. Colorimetric and atomic absorption spectrometric determination of mucolytic drug ambroxol through ion-pair formation with iron and thiocyanate.

    Science.gov (United States)

    Levent, Abdulkadir; Sentürk, Zühre

    2010-09-01

    Colorimetric and atomic absorption spectrometric methods have been developed for the determination of mucolytic drug Ambroxol. These procedures depend upon the reaction of iron(III) metal ion with the drug in the presence of thiocyanate ion to form stable ion-pair complex which extractable chloroform. The red-coloured complex was determined either colorimetrically at 510 nm or by indirect atomic absorption spectrometry (AAS) via the determination of the iron content in the formed complex. The optimum experimental conditions for pH, concentrations of Fe(3+) and SCN(-), shaking time, phase ratio, and the number of extractions were determined. Under the proposed conditions, linearity was obeyed in the concentration ranges 4.1x10(-6) - 5.7x10(-5) M (1.7-23.6 µg mL(-1)) using both methods, with detection limits of 4.6x10(-7) M (0.19 µg mL(-1)) for colorimetry and 1.1x10(-6) M (0.46 µg mL(-1)) for AAS. The proposed methods were applied for the determination of Ambroxol in tablet dosage forms. The results obtained were statistically analyzed and compared with those obtained by applying the high-performance liquid chromatographic method with diode-array detection.

  15. Remote mass spectrometric sampling of electrospray- and desorption electrospray-generated ions using an air ejector.

    Science.gov (United States)

    Dixon, R Brent; Bereman, Michael S; Muddiman, David C; Hawkridge, Adam M

    2007-10-01

    A commercial air ejector was coupled to an electrospray ionization linear ion trap mass spectrometer (LTQ) to transport remotely generated ions from both electrospray (ESI) and desorption electrospray ionization (DESI) sources. We demonstrate the remote analysis of a series of analyte ions that range from small molecules and polymers to polypeptides using the AE-LTQ interface. The details of the ESI-AE-LTQ and DESI-AE-LTQ experimental configurations are described and preliminary mass spectrometric data are presented.

  16. Mass spectrometric identification of proteins and characterization of their post-translational modifications in proteome analysis

    DEFF Research Database (Denmark)

    Roepstorff, P; Larsen, Martin Røssel

    2001-01-01

    dominant strategies for identification of proteins from gels based on peptide mass spectrometric fingerprinting and partial sequencing by mass spectrometry are described. After identification of the proteins the next challenge in proteome analysis is characterization of their post-translational...... modifications. The general problems associated with characterization of these directly from gel separated proteins are described and the current state of art for the determination of phosphorylation, glycosylation and proteolytic processing is illustrated....

  17. A Spectrometric Setup for Synchronous Total Internal Reflection Fluorescence Measurement at the Solid/Liquid Interface

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A spectrometric setup to perform total internal reflection fluorescence (TIRF) and synchronous TIRF measurements at solid/liquid interfaces is presented. The combination of TIRF and synchronous fluorescence was proposed to analyze simultaneously different components at interfaces. The TIRF excitation, emission and synchronous spectra of a water-soluble porphyrin were obtained from water/glass interface using this setup without the existence of a surfactant.

  18. Characterize Glyphosate Residues in Wuyi Rock Tea Using HPLC Tandem Mass Spectrometric Method%高效液相色谱串联质谱测定武夷岩茶中草甘膦残留量的方法探讨

    Institute of Scientific and Technical Information of China (English)

    衷兴旺

    2014-01-01

    A method for determination of glyphosate residues in Wuyi rock tea was developed using high performance liquid chromatography tandem mass spectrometry method. The procedure is as follow,the glyphosate were extracted with water from samples, and purified using TPT. Then derivatization reaction was done in borate buffer with fluorenylmethylchloroformate(FMOC - Cl). Using 1% solution of ammonium acetate and acetonitrile as the mobile phase, mass spectrometry using electrospray ionization in positive ionization mode and multiple reaction monitoring mode. The results showed that the linear correlation coefficient r = 0. 998 when glyphosate is between1ng - 10ng/ mL. Wuyi blank samples were used in added recovery experiment at four spiked levels(n = 5),the average recovery of glyphosate were 87. 3% to 98. 0% . The relative standard deviation(RSD)were 3. 46 to 5. 12.%采用高效液相色谱串联质谱建立了武夷岩茶样品中草甘膦的残留量的测定方法。样品经水固相萃取和茶叶专用萃取柱(TPT)净化后,在硼酸盐缓冲液中与9-芴甲基氯甲酸酯(FMOC - Cl)进行衍生化反应,以1%乙酸铵溶液和乙腈为流动相,质谱检测采用电喷雾正离子化模式和多反应监测模式。结果表明,草甘膦在1~10 ng/ mL 范围内线性良好,线性相关系数 r =0.998。通过对空白武夷岩茶样品进行4个加标水平的添加回收实验(n =5),草甘膦的平均回收率和相对标准偏差(RSD)分别为87.3%~98.0%和3.46~5.12。

  19. 基于差分吸收激光雷达的一种新的对流层臭氧浓度反演算法%Butanol Extraction Combined with Dilute Hydrochloric Acid Dissolution-Atomic Fluorescence Spectrometric Method for Indirect Determination of Molybdenum in Chinese Herbal Medicine

    Institute of Scientific and Technical Information of China (English)

    范广强; 刘建国; 刘文清; 陆亦怀; 张天舒; 董云升; 赵雪松

    2012-01-01

    A method for indirectly determining the molybdenum in Chinese herbal medicine by butanol extraction and dilute hydrochloric acid dissolution was established for atomic fluorescence spectrometry. The molybdoarsenate heteropoly acid, formed in the presence of As( V) and ammonium molybdate in 0. 3 mol · L-1 sulphuric acid medium, was separated and enriched in the organic solvent, then the evaporation of organic reagent was implemented and the left residue was dissolved in dilute hydrochloric acid in which the arsenic content was determined on behalf of molybdenum. In the optimum experimental conditions, molybdenum content in 0~15 μg · L-1 range depicts a good linear relationship, the detection limit and relative standard deviation of 0. 44 μg · L-1 and 1.1% were obtained, respectively. Spiked Chinese herbal medicine samples were determined with the proposed method, and recoveries of 95. 6%—101. 3% were achieved.%差分吸收激光雷达探测对流层臭氧浓度时,气溶胶的干扰会造成较大的误差.提出了一种算法,该算法能够同时反演得到对流层臭氧浓度和气溶胶消光系数,减少气溶胶对反演结果的影响.使用实验数据,分析计算了气溶胶雷达比,气溶胶波长指数、标定点气溶胶后向散射比各种变化参数对反演结果的误差.结果表明,1km以下,各种变化参数造成的反演误差小于8%,1km以上臭氧浓度误差主要来源于信号和背景噪声,各种参数反演误差小于3%.最后给出了利用该算法得到对流层臭氧浓度和气溶胶的消光系数垂直廓线,并和传统的双波长差分算法反演结果作了比较分析.实验结果表明该算法是可行的,该算法可以减少气溶胶对差分吸收激光雷达测量结果引起的误差.

  20. Mass-spectrometric exploration of proteome structure and function

    DEFF Research Database (Denmark)

    Aebersold, Ruedi; Mann, Matthias

    2016-01-01

    , the structures and functions of selected proteins have been studied using biochemical and biophysical methods. However, the properties and behaviour of the proteome as an integrated system have largely remained elusive. Powerful mass-spectrometry-based technologies now provide unprecedented insights...

  1. Characterization of used lubricating oil by spectrometric techniques

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Andressa Moreira de, E-mail: andressa@ctaa.embrapa.br [Embrapa Agroindustria de Alimentos, Guaratiba, Rio de Janeiro, RJ (Brazil); Correa, Sergio Machado [Faculdade de Engenharia. Universidade do Estado do Rio de Janeiro (UERJ), Resende, RJ (Brazil); Silva, Glauco Correa da [Instituto de Engenharia Nuclear (IEN/CNEN-RJ), Rio de Janeiro, RJ (Brazil)

    2011-07-01

    Full text: The engine lubricating oil drags all kinds of impurities generated by wear of internal components. Thus, it is necessary to monitor the physical and chemical properties and concentration of metals in lubricants used to determine the appropriate time to replace them. Moreover, one can monitor the wear of the engines through the levels of metals in oils. To achieve these goals, some detection techniques such as Flame atomic absorption spectrometry (FAAS), Inductively coupled plasma optical emission spectrometry (ICP-OES) and X-ray fluorescence (XRF), have been widely used to determine metals in lubricating oils and also in other oil derivatives. Thus, some of these techniques were used in this study. Also the technique used was Gas chromatography mass spectrometry (GC / MS) for characterization of chromatographic profile of the engine lubricating oil after use. Through the technique of ICP-OES for method of United States Environmental Protection Agency (USEPA) METHOD 6010B - Inductively coupled plasma optical emission spectrometry was performed to characterize metals in lubricating oil motor, using equipment from ICP-OES Perkin-Elmer{sup R} OPTIMA 3000 ICP-Winlab and software, obtaining the following identification of metals: barium (Ba), calcium (Ca), lead (Pb), copper (Cu), Chromium (Cr), iron (Fe), magnesium (Mg), molybdenum (Mo) and zinc (Zn). Using the XRF technique, through the equipment EDFRX Shimadzu{sup R} model 800HS EDX, Rh tube, applied voltage of 50kV, amperage 100{mu}A, detector Si (Li) cooled with liquid nitrogen and collimator 10mm, we analyzed all the components comprised in the range of Ti to U and Na to SC, identified the following metals: calcium (Ca), zinc (Zn), iron (Fe), copper (Cu), molybdenum (Mo) and nickel (Ni). The characterization was performed by chromatographic methods: USEPA METHOD 5021A - Volatile organic compounds in various sample matrices using equilibrium headspace analysis, USEPA METHOD 8015B - Nonhalogenated Organics

  2. Separation of silver ions and starch modified silver nanoparticles using high performance liquid chromatography with ultraviolet and inductively coupled mass spectrometric detection

    Energy Technology Data Exchange (ETDEWEB)

    Hanley, Traci A.; Saadawi, Ryan; Zhang, Peng; Caruso, Joseph A., E-mail: joseph.caruso@uc.edu; Landero-Figueroa, Julio

    2014-10-01

    The production of commercially available products marketed to contain silver nanoparticles is rapidly increasing. Species-specific toxicity is a phenomenon associated with many elements, including silver, making it imperative to develop a method to identify and quantify the various forms of silver (namely, silver ions vs. silver nanoparticles) possibly present in these products. In this study a method was developed using high performance liquid chromatography (HPLC) with ultraviolet (UV–VIS) and inductively coupled mass spectrometric (ICP-MS) detection to separate starch stabilized silver nanoparticles (AgNPs) and silver ions (Ag{sup +}) by cation exchange chromatography with 0.5 M nitric acid mobile phase. The silver nanoparticles and ions were baseline resolved with an ICP-MS response linear over four orders of magnitude, 0.04 mg kg{sup −1} detection limit, and 90% chromatographic recovery for silver solutions containing ions and starch stabilized silver nanoparticles smaller than 100 nm.

  3. Separation of silver ions and starch modified silver nanoparticles using high performance liquid chromatography with ultraviolet and inductively coupled mass spectrometric detection

    Science.gov (United States)

    Hanley, Traci A.; Saadawi, Ryan; Zhang, Peng; Caruso, Joseph A.; Landero-Figueroa, Julio

    2014-10-01

    The production of commercially available products marketed to contain silver nanoparticles is rapidly increasing. Species-specific toxicity is a phenomenon associated with many elements, including silver, making it imperative to develop a method to identify and quantify the various forms of silver (namely, silver ions vs. silver nanoparticles) possibly present in these products. In this study a method was developed using high performance liquid chromatography (HPLC) with ultraviolet (UV-VIS) and inductively coupled mass spectrometric (ICP-MS) detection to separate starch stabilized silver nanoparticles (AgNPs) and silver ions (Ag+) by cation exchange chromatography with 0.5 M nitric acid mobile phase. The silver nanoparticles and ions were baseline resolved with an ICP-MS response linear over four orders of magnitude, 0.04 mg kg- 1 detection limit, and 90% chromatographic recovery for silver solutions containing ions and starch stabilized silver nanoparticles smaller than 100 nm.

  4. Metallomics investigations on potential binding partners of methylmercury in tuna fish muscle tissue using complementary mass spectrometric techniques.

    Science.gov (United States)

    Kutscher, Daniel J; Sanz-Medel, Alfredo; Bettmer, Jörg

    2012-08-01

    In this study, the binding behaviour of methylmercury (MeHg(+)) towards proteins is investigated. Free sulfhydryl groups in cysteine residues are known to be the most likely binding partners, due to the high affinity of mercury to sulphur. However, detailed knowledge about discrete binding sites in living organisms has been so far scarce. A metallomics approach using different methods like size-exclusion chromatography (SEC) and liquid chromatography (LC) coupled to inductively coupled plasma-mass spectrometry (ICP-MS) as well as complementary mass spectrometric techniques (electrospray ionisation-tandem mass spectrometry, ESI-MS/MS) are combined to sequence and identify possible target proteins or peptides after enzymatic digestion. Potential targets for MeHg(+) in tuna fish muscle tissue are investigated using the certified reference material CRM464 as a model tissue. Different extraction procedures appropriate for the extraction of proteins are evaluated for their efficiency using isotope dilution analysis for the determination of total Hg in the extracts. Due to the high chemical stability of the mercury-sulphur bond, the bioconjugate can be quantitatively extracted with a combination of tris(hydroxymethyl)aminomethane (TRIS) and sodium dodecyl sulphate (SDS). Using different separation techniques such as SEC and SDS-polyacrylamide gel electrophoresis (SDS-PAGE) it can be shown that major binding occurs to a high-molecular weight protein (M(w) > 200 kDa). A potential target protein, skeletal muscle myosin heavy chain, could be identified after tryptic digestion and capillary LC-ESI-MS/MS.

  5. Investigation of the mouse cerebellum using STIM and {mu}-PIXE spectrometric and FTIR spectroscopic mapping and imaging

    Energy Technology Data Exchange (ETDEWEB)

    Hackett, M.J. [School of Chemistry, University of Sydney, NSW 2006 (Australia); Siegele, R., E-mail: rns@ansto.gov.au [Institute for Environmental Research, Australian Nuclear Science and Technology Organisation, Lucas Heights NSW 2234 (Australia); El-Assaad, F. [Vascular Immunology Unit, Bosch Institute and School of Medical Sciences, University of Sydney, NSW 2006 (Australia); McQuillan, J.A. [Molecular Immunopathology Unit, Bosch Institute and School of Medical Sciences, University of Sydney, NSW 2006 (Australia); Aitken, J.B.; Carter, E.A. [School of Chemistry, University of Sydney, NSW 2006 (Australia); Grau, G.E. [Vascular Immunology Unit, Bosch Institute and School of Medical Sciences, The University of Sydney, NSW 2006 (Australia); Hunt, N.H. [Molecular Immunopathology Unit, Bosch Institute and School of Medical Sciences, The University of Sydney, NSW 2006 (Australia); Cohen, D. [Institute for Environmental Research, Australian Nuclear Science and Technology Organisation, Lucas Heights NSW 2234 (Australia); Lay, P.A. [School of Chemistry, The University of Sydney, NSW 2006 (Australia)

    2011-10-15

    The cerebral biochemistry associated with the development of many neurological diseases remains poorly understood. In particular, incomplete understanding of the mechanisms through which vascular inflammation manifests in tissue damage and altered brain function is a significant hindrance to the development of improved patient therapies. To this extent, a combination of spectrometric/spectroscopic mapping/imaging methods with an inherent ability to provide a wealth of biochemical and physical information have been investigated to understand further the pathogenesis of brain disease. In this study, proton-induced X-ray emission (PIXE) mapping was combined with scanning transmission ion microscopy (STIM) mapping and Fourier-transform infrared (FTIR) imaging of the same tissue sample to study directly the composition of the murine (mouse) cerebellum. The combination of the elemental, density and molecular information provided by these techniques enabled differentiation between four specific tissue types within the murine cerebellum (grey matter, white matter, molecular layer and micro blood vessels). The results presented are complementary, multi-technique measurements of the same tissue sample. They show elemental, density and molecular differences among the different tissue types.

  6. Distribution of coniferin in differentiating normal and compression woods using MALDI mass spectrometric imaging coupled with osmium tetroxide vapor treatment.

    Science.gov (United States)

    Yoshinaga, Arata; Kamitakahara, Hiroshi; Takabe, Keiji

    2016-05-01

    Matrix-assisted laser desorption/ionization mass spectrometric imaging (MALDI-MSI) was employed to detect monolignol glucosides in differentiating normal and compression woods of two Japanese softwoods, Chamaecyparis obtusa and Cryptomeria japonica Comparison of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry collision-induced dissociation fragmentation analysis and structural time-of-flight (MALDI-TOF CID-FAST) spectra between coniferin and differentiating xylem also confirmed the presence of coniferin in differentiating xylem. However, as matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and MALDI-TOF CID-FAST spectra of sucrose were similar to those of coniferin, it was difficult to distinguish the distribution of coniferin and sucrose using MALDI-MSI and collision-induced dissociation measurement only. To solve this problem, osmium tetroxide vapor was applied to sections of differentiating xylem. This vapor treatment caused peak shifts corresponding to the introduction of two hydroxyl groups to the C=C double bond in coniferin. The treatment did not cause a peak shift for sucrose, and therefore was effective in distinguishing coniferin and sucrose. Thus, it was found that MALDI-MSI combined with osmium tetroxide vapor treatment is a useful method to detect coniferin in differentiating xylem.

  7. Near-infrared spectrometric determination of dipyrone in closed ampoules.

    Science.gov (United States)

    Sanches, Fátima Aparecida C; Abreu, Rosimeri B; Pontes, Márcio José Coelho; Leite, Flaviano C; Costa, Daniel Jackson E; Galvão, Roberto Kawakami H; Araujo, Mario Cesar U

    2012-04-15

    The present paper proposes an analytical method for fast near-infrared (NIR) determination of dipyrone in injectable formulations with a nominal content of 50.0%mv(-1) without violation of the ampoule. For this purpose, two multivariate calibration methods are evaluated, namely Partial-Least-Squares (PLS) and Multiple Linear Regression (MLR) with variable selection by the Successive Projections Algorithm (SPA). The resulting models comprised four latent variables (PLS) and five spectral variables (MLR-SPA). Appropriate predictions were obtained in both cases, with RMSEP values of 0.39 (PLS) and 0.35%mv(-1) (MLR-SPA) and correlation coefficients of 0.9970 (PLS) and 0.9975 (MLR-SPA) for a calibration range of 40-60%mv(-1). No systematic error was observed and no significant differences were found between the predicted and reference values, according to a paired t-test at 95% confidence level.

  8. Mass-spectrometric REE analysis in sulphide minerals

    Directory of Open Access Journals (Sweden)

    Irina R. Elizarova

    2012-01-01

    Full Text Available The standard samples of diorite, granite and anorthosite (National Centre for Petrographic and Geochemical Research (CRPG CNRS, Nancy, France were analyzed to measure rare-earth element (REE concentrations by the ICP MS method (quadrupole ELAN 9000 DRC-e without preliminary dilution and concentration procedures. The certified values of REE concentrations measured on ELEMENT-2 mass-spectrometer by ICP MS method in Nancy are also well reproduced on ELAN 9000. The mass-spectrometer analytical environment and modes of operation were adjusted to detect REE in sulphide minerals by the example of the pyrite from the PGE Penikat layered intrusion (Finland and chalcopyrite from the Talnakh deposit (Kazakhstan. The total REE content in the pyrite is ca. 3.5 ppm, that is enough to establish Sm-Nd age of pyrite. By the example of State Standard Sample 2463 (Apatite, Russia it is shown how to apply the mineral/chondrite spectra to evaluate the accuracy of the REE analytical results.

  9. Malevolent use of radioactive materials: An international exercise in the analysis of gamma-spectrometric data

    DEFF Research Database (Denmark)

    Dowdall, M.; Andersson, Kasper Grann; Palsson, S.E.

    2010-01-01

    with isotopes and activities that present significant challenges with respect to identification and quantification using gamma ray spectrometry. The MALRAD international exercise was designed to provide a practice opportunity for authorities and laboratories to work with synthetic gamma-spectrometric data...... isotopes, irrespective of the detector type involved, all participants were in a position to identify sources and provide estimates of activity. For situations involving shielded sources or special nuclear materials most participants were in a position to provide indications as to what the sources were...

  10. Electron Ionization Mass Spectrometric Study of Some Substituted 1,3-oxazoles

    OpenAIRE

    Salgueiro, Pedro; Dias, Catarina; Carreiras, M. Carmo; Borges, Carlos

    2007-01-01

    Comunicação oral sob a forma painel Heterocyclic compounds are widely used as pharmaceuticals. Tacrine (THA) was the first drug approved for the treatment of Alzheimer’s disease (AD) and a great effort has been made to design and synthesize new THA-analogues in order to evaluate their beneficial effects as therapeutic agents in this disease.1-6 Contrasting with the pharmaceutical interest, mass spectrometric studies of these compounds and of some of its precursors, namely the oxazole and o...

  11. Tandem mass spectrometric fragmentation patterns of known and new steviol glycosides with structure proposals.

    Science.gov (United States)

    Zimmermann, Benno F

    2011-06-15

    Stevia rebaudiana contains several steviol glycosides that have a sweet flavor. They are up to 450 times sweeter than sucrose, but some have an undesirable aftertaste. Up to 2010, ten different steviol glycosides have been described from the leaves or purified extracts of S. rebaudiana. In this paper, the tandem mass spectrometric fragmentation patterns of these ten compounds are compiled, along with a scheme for structural elucidation. This scheme is then applied to 12 steviol glycosides that have not yet been described. The proposed structures of five steviol glycosides have been confirmed by other authors.

  12. 静态顶空-气相色谱质谱选择性测定烟用白乳胶中7种苯系物%Selective determination of seven benzene series components in cigarette adhesives by static headspace gas chromatograph-mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    姬厚伟; 刘剑; 叶冲; 万强; 韩伟; 王芳; 杨虹杰; 杨敬国

    2012-01-01

    为选择性测定烟用白乳胶中7种苯系物,建立了静态顶空-气相色谱质谱选择离子定量的测定方法.样品经140℃、30 min静态顶空后,以2-己酮为内标,采用HP-INNOWAX柱,气相色谱-质谱选择离子模式检测,内标法定量.该方法对7种苯系物的定量检测限为0.008 ~0.01 mg/kg,加标回收率为88.9%-104.5%,RSD <5%,效果良好.%A method based on static headspace gas chromatography-mass spectrometry ( SHS-GC/MS) and internal standard was developed to selectively determine seven benzene series components contents in cigarette adhesive. Experimental conditions such as headspace temperature, headspace time and analytical conditions of GC-MS were optimized. Cigarette adhesive samples were treated at 140℃ for 30 min. Head-space vapor of final extraction was injected into a HP-INNOWAX column and detected by MS. The target compounds were quantified by internal standard method under selected ion monitoring mode. Results showed that; the recoveries ranged from 88.9% to 104.5% , with relative standard deviations ( RSDs) e less than 5%. The linear range was from 0.01 to 0.5 μg/mL with a good, linear determination coefficient (R2 >0.999) and limits of quantification were 0.008 ~0.0lmg/kg. The method is accurate, simple and rapid.

  13. Detection of Candida albicans by mass spectrometric fingerprinting.

    Science.gov (United States)

    Zehm, Sarah; Schweinitz, Simone; Würzner, Reinhard; Colvin, Hans Peter; Rieder, Josef

    2012-03-01

    Candida albicans is one of the most frequent causes of fungal infections in humans. Significant correlation between candiduria and invasive candidiasis has previously been described. The existing diagnostic methods are often time-consuming, cost-intensive and lack in sensitivity and specificity. In this study, the profile of low-molecular weight volatile compounds in the headspace of C. albicans-urine suspensions of four different fungal cell concentrations compared to nutrient media and urine without C. albicans was determined using proton-transfer reaction mass spectrometry (PTR-MS). At fungal counts of ≥1.5 × 10(5) colony forming units (CFU)/ml signals at 45, 47 and 73 atomic mass units (amu) highly significantly increased. At fungal counts of albicans-urine suspensions of different fungal cell concentrations. PTR-MS represents a promising approach to rapid, highly sensitive and non-invasive clinical diagnostics allowing qualitative and quantitative analysis.

  14. MALDI-TOF mass spectrometric identification of dyes and pigments.

    Science.gov (United States)

    Soltzberg, L J; Hagar, Amanda; Kridaratikorn, Supicha; Mattson, Anne; Newman, Richard

    2007-11-01

    We have used MALDI-TOF mass spectrometry to characterize a selection of dyes from the Schweppe dye collection and pigments from the Tate Gallery collection. MALDI-TOF mass spectra of such samples are easily obtained and, through observation of both positive and negative ion spectra, provide a convenient, versatile method for dye characterization and identification. Such pairs of positive and negative ion spectra immediately distinguish between acidic and basic dyes and provide the characteristic mass of either the molecular ion or a simply related fragment ion. This approach is especially useful in situations where very small amounts of analyte are available, as in museum research and forensic analysis. In the case of textile dyes, we have carried out identification on material from single fibers and, with insoluble pigments, have begun to identify components of historically important pastel sticks from submicrogram samples.

  15. Mass spectrometric identification of hemoglobin modifications induced by nitrosobenzene.

    Science.gov (United States)

    Di Girolamo, Francesco; Campanella, Luigi; Samperi, Roberto; Bachi, Angela

    2009-07-01

    Aniline and nitrobenzene (NB) are widely used industrial chemicals. Early effects of aniline toxicity include methemoglobin formation and damage to erythrocytes (Jenkins, F.P., 1972. The no-effect dose of anilne in human subjects and a comparison of aniline toxicity in man and rat. Food Cosmet. Toxicol. 10, 671-679; Bus, J.S., Popp, J.A., 1987. Perspectives on the mechanism of action of the splenic toxicity of aniline and structurally-related. Food Chem. Toxicol. 25, 619-627). In this report, we describe an analytical method, based on LC techniques and mass spectrometry, which could help in monitoring the exposure to aniline and NB. In particular, we describe and characterize the formation of specific adducts during an in vitro reaction of nitrosobenzene (NOB), the main metabolite of aniline and NB, and human hemoglobin.

  16. Analytical Methodologies for Semiconductor Process Characterization—Novel Mass Spectrometric Methods

    Science.gov (United States)

    Vartanian, Victor H.; Goolsby, Brian

    2003-09-01

    New analytical techniques and applications are needed to address the challenges facing the semiconductor industry as transistor feature sizes continue to decrease beyond the 100 nm technology node. Several new applications of quadrupole ion trap (QIT) and Fourier transform ion cyclotron resonance (FTICR) mass spectrometry are presented, specifically applied to process tool effluent characterization. A QIT with atmospheric pressure transfer line and pneumatically driven valves is used to characterize a dielectric etch process, with response times comparable to extractive Fourier transform infrared (FTIR) spectroscopy. The QIT allows application of collision-induced dissociation (CID) for structure elucidation, and is useful when high-molecular weight metal organic precursors are used in processes that evolve byproducts that are ambiguous by gas-phase infrared analysis. Similarly, a transportable FTICR with a fixed magnet and pulsed-valve sample introduction allows matrix ion ejection to improve the sensitivity to analyte ions. The FTICR has also been evaluated for a low-pressure chemical vapor deposition (LPCVD) process using a high-molecular weight precursor. Byproducts are ambiguous in FTIR spectra, but the FTICR provided structural confirmation of the effluent species, and is a useful complement to FTIR. The FTICR was also used with FTIR to characterize process tool effluent emissions in a study using SF6 and Ar to plasma etch a candidate metal oxide gate electrode material, RuO2. The results confirmed that no significant amount of RuO4, a toxic byproduct, were produced in this process.

  17. Electrospray ionization mass spectrometric method for the determination of cannabinoid precursors

    DEFF Research Database (Denmark)

    Hansen, H.H.; Hansen, S.H.; Bøjrnsdottir, I.

    1999-01-01

    N-Acylethanolamine phospholipids (NAPEs) serve as endogenous precursors of N-acylethanolamines (NAEs), e.g. N-arachidonoylethanolamine (anandamide) and N-palmitoylethanolamine that are endogenous ligands of cannabinoid receptors. Under physiological conditions, NAPE is found in very low...

  18. Mass spectrometric methods prove the use of beeswax and ruminant fat in late Roman cooking pots.

    Science.gov (United States)

    Kimpe, K; Jacobs, P A; Waelkens, M

    2002-08-30

    Lipid extracts of sherds of archaeological late Roman cooking pots were analysed using high temperature-gas chromatography coupled to a mass spectrometer and liquid chromatography with atmospheric pressure chemical ionization mass spectrometer detection (LC-APCI-MS). With these advanced techniques the use of beeswax was shown through identification of the constituting alkanes, mono and diesters. The detection of high amounts of saturated triacylglycerols (TAGs) further indicated that animal fat was processed in these pots. Part of the animal fat was characterised as originating from ruminants due to the presence of trans-fatty acids. The distribution of saturated TAGs and the higher concentration of stearic acid compared to palmitic acid in the transesterified lipid extract indicated that this was sheep fat. The results illustrate how complex mixtures can be unravelled and original contents of ancient ceramic vessels can be determined using specialised analytical equipment.

  19. Distinguishing Aspartic and Isoaspartic Acids in Peptides by Several Mass Spectrometric Fragmentation Methods

    Science.gov (United States)

    DeGraan-Weber, Nick; Zhang, Jun; Reilly, James P.

    2016-12-01

    Six ion fragmentation techniques that can distinguish aspartic acid from its isomer, isoaspartic acid, were compared. MALDI post-source decay (PSD), MALDI 157 nm photodissociation, tris(2,4,6-trimethoxyphenyl)phosphonium bromide (TMPP) charge tagging in PSD and photodissociation, ESI collision-induced dissociation (CID), electron transfer dissociation (ETD), and free-radical initiated peptide sequencing (FRIPS) with CID were applied to peptides containing either aspartic or isoaspartic acid. Diagnostic ions, such as the y-46 and b+H2O, are present in PSD, photodissociation, and charge tagging. c•+57 and z-57 ions are observed in ETD and FRIPS experiments. For some molecules, aspartic and isoaspartic acid yield ion fragments with significantly different intensities. ETD and charge tagging appear to be most effective at distinguishing these residues.

  20. Three-dimensional interferometric, spectrometric, and planetary views of Procyon

    CERN Document Server

    Chiavassa, A; Kervella, P; Matter, A; Lopez, B; Collet, R; Magic, Z; Asplund, M

    2012-01-01

    We used a new realistic 3D radiative-hydrodynamical model atmosphere of Procyon generated with the Stagger Code and synthetic spectra computed with the radiative transfer code Optim3D to re-analyze interferometric and spectroscopic data from the optical to the infrared of Procyon. We compute intensity maps in two optical filters centered at 500 and 800 nm (MARK III) and one infrared filter centered at 2200 nm (VINCI). We constructed stellar disk images accounting for the center-to-limb variations and used them to derive visibility amplitudes and closure phases. We provide 3D limb-darkening coefficients in the optical as well as in the infrared. We show that visibility curves and closure phases show clear deviations from circular symmetry from the 3rd lobe on. These deviations are detectable with current interferometers using closure phases. We derive new angular diameters at different wavelengths with two independent methods based on 3D simulations. We find a diameter_Vinci = 5.390 \\pm 0.03 mas that this is c...

  1. High-throughput mass spectrometric cytochrome P450 inhibition screening.

    Science.gov (United States)

    Lim, Kheng B; Ozbal, Can C; Kassel, Daniel B

    2013-01-01

    We describe here a high-throughput assay to support rapid evaluation of drug discovery compounds for possible drug-drug interaction (DDI). Each compound is evaluated for its DDI potential by incubating over a range of eight concentrations and against a panel of six cytochrome P450 (CYP) enzymes: 1A2, 2C8, 2C9, 2C19, 2D6, and 3A4. The method utilizes automated liquid handling for sample preparation, and online solid-phase extraction/tandem mass spectrometry (SPE/MS/MS) for sample analyses. The system is capable of generating two 96-well assay plates in 30 min, and completes the data acquisition and analysis of both plates in about 30 min. Many laboratories that perform the CYP inhibition screening automate only part of the processes leaving a throughput bottleneck within the workflow. The protocols described in this chapter are aimed to streamline the entire process from assay to data acquisition and processing by incorporating automation and utilizing high-precision instrument to maximize throughput and minimize bottleneck.

  2. Characterisation of organic and conventional sweet basil leaves using chromatographic and flow-injection mass spectrometric (FIMS) fingerprints combined with principal component analysis.

    Science.gov (United States)

    Lu, Yingjian; Gao, Boyan; Chen, Pei; Charles, Denys; Yu, Liangli Lucy

    2014-07-01

    Sweet basil, Ocimum basilicum, is one of the most important and wildly used spices and has been shown to have antioxidant, antibacterial, and anti-diarrheal activities. In this study, high performance liquid chromatographic (HPLC) and flow-injection mass spectrometric (FIMS) fingerprinting techniques were used to differentiate organic and conventional sweet basil leaf samples. Principal component analysis (PCA) of the fingerprints indicated that both HPLC and FIMS fingerprints could effectively detect the chemical differences in the organic and conventional sweet basil leaf samples. This study suggested that the organic basil sample contained greater concentrations of almost all the major compounds than its conventional counterpart on a per same botanical weight basis. The FIMS method was able to rapidly differentiate the organic and conventional sweet basil leaf samples (1min analysis time), whereas the HPLC fingerprints provided more information about the chemical composition of the basil samples with a longer analytical time.

  3. Seasonal variations of bisphenol A in the Danube River by the municipality of Novi Sad, Serbia

    Directory of Open Access Journals (Sweden)

    Milanović Maja

    2016-01-01

    Full Text Available Seasonal variations of bisphenol A (BPA were investigated in the Danube along the Novi Sad bank, Serbia using solid-phase extraction followed by gas chromatographic mass spectrometric method. The obtained results confirmed the presence of BPA above the limit of quantification (6 ng/L in 22 out of 32 water samples at all eight sampling sites. Тhe BPA concentration varied from 1 for autumn, spring and summer. The high potential risk which is attributed to the elevated summer concentrations is probably the result of the increased human activates and weather conditions. [Projekat Ministarstva nauke Republike Srbije, br. III46009

  4. 氯霉素类三甲基硅衍生物的质谱特征及其残留监测

    Institute of Scientific and Technical Information of China (English)

    贺利民; 曾振灵; 刘雅红; 陈建新; 黄显会

    2004-01-01

    Mass characteristics of TMS derivative of chloramphenicol, florfenicol,and thiamphenicol were interpreted manually, respectively. Then SIM mode was performed at m/z 225, m/z 242, m/z 244, m/z 361 for CAP, m/z 178, m/z 257, m/z 259, m/z 394 for FF,and m/z 242, m/z 244, m/z 257, m/z 330 for TAP. A sensitive, reproducible gas chromatographic-mass spectrometric method was developed for simultaneous monitoring residues of fenicols in pork and tissues.

  5. Identification and quantification of flavonoids in human urine samples by column switching liquid chromatography coupled to atmospheric pressure chemical ionization mass spectrometry

    DEFF Research Database (Denmark)

    Nielsen, Salka E.; Freese, R.; Cornett, C.

    2000-01-01

    A rapid and sensitive high-performance liquid chromatographic mass spectrometric (HPLC-MS) method is described for the determination and quantification of 12 dietary flavonoid glycosides and aglycons in human urine samples. Chromatographic separation of the analytes of interest was achieved...... by column-switching, using the first column (a Zorbax 300SB C-3 column) for sample cleanup and eluting the heart-cut flavonoid fraction onto the second column (a Zorbax SE C-18 column) for separation and detection by ultraviolet and atmospheric pressure chemical ionization MS using single ion monitoring...... with high and low flavonoid content was analyzed, and the results are reported....

  6. Storage and retrieval of mass spectral information

    Science.gov (United States)

    Hohn, M. E.; Humberston, M. J.; Eglinton, G.

    1977-01-01

    Computer handling of mass spectra serves two main purposes: the interpretation of the occasional, problematic mass spectrum, and the identification of the large number of spectra generated in the gas-chromatographic-mass spectrometric (GC-MS) analysis of complex natural and synthetic mixtures. Methods available fall into the three categories of library search, artificial intelligence, and learning machine. Optional procedures for coding, abbreviating and filtering a library of spectra minimize time and storage requirements. Newer techniques make increasing use of probability and information theory in accessing files of mass spectral information.

  7. A method for determination of methyl chloride concentration in air trapped in ice cores.

    Science.gov (United States)

    Saito, Takuya; Yokouchi, Yoko; Aoki, Shuji; Nakazawa, Takakiyo; Fujii, Yoshiyuki; Watanabe, Okitsugu

    2006-05-01

    A method for measuring the concentration of methyl chloride (CH3Cl) in air trapped in an ice core was developed. The method combines the air extraction by milling the ice core samples under vacuum and the analysis of the extracted air with a cryogenic preconcentration/gas chromatograph/mass spectrometry system. The method was applied to air from Antarctic ice core samples estimated to have been formed in the pre-industrial and/or early industrial periods. The overall precision of the method deduced from duplicate ice core analyses was estimated to be better than +/-20 pptv. The measured CH3Cl concentration of 528+/-26 pptv was similar to the present-day concentration in the remote atmosphere as well as the CH3Cl concentration over the past 300 years obtained from Antarctic firn air and ice core analyses.

  8. Thermal Desorption-Gas Chromatography or Gas Chromatograph-Mass Spectrometry for Analysis of Semi-Volatile Compounds on Atmospheric Particulate Matters%热解析-气相色谱或气相色谱-质谱法分析大气可吸入颗粒物中的半挥发性有机化合物

    Institute of Scientific and Technical Information of China (English)

    孟虎; 赵景红; 段春凤; 郝亮; 关亚风

    2014-01-01

    A thermal desorption ( TD) device was developed and coupled to gas chromatography ( GC) or gas chromatography-mass spectrometry ( GC-MS ) for the qualitative and quantitative analysis of semi-volatile organic compounds on atmospheric particulate matters ( PM ) . The TD was operated by direct heating and placed on the GC injector, leading to high heating rate and easy transfer of analytes to GC without focusing of analytes by cold trap. For establishing the TD-GC method, the materials used for supporting PM samples, temperature and time of thermal desorption, and types of sample injection were investigated for detection of sixteen polycyclic aromatic hydrocarbons ( PAHs) and nine n-alkanes. The limits of detection of the proposed TD-GC method were in the range of 0. 014-0. 093 ng for PAHs, and 0. 016-0. 026 ng for n-alkanes, respectively, with the correlation coefficients of correlation above 0. 9975. The TD-GC method was applied to the determination of trace PAHs and n-alkanes on PM10 samples from three cities. The recoveries were in the range of 95%-135% ( PAHs) and 95%-115% ( n-alkanes) , respectively. Finally, the TD was coupled to GC-MS for comparison of the contents of PAHs and n-alkanes on PMx with different particulate size ( x=10 , 5, 2, 1, 0. 5, 0. 25, 0. 1).%研制了一种热解析装置,并与气相色谱或气相色谱-质谱联用,定性定量分析了大气可吸入颗粒物中的半挥发性有机物。装置为直热式加热,升温速率快;直接安装在色谱进样器上方,无需冷阱聚焦。将热解析装置与气相色谱联用,优化了样品承载体材质、热解析条件和进样模式,并用于16种多环芳烃和9种正构烷烃的检测。结果表明,热解析-气相色谱方法对多环芳烃和正构烷烃的检出限分别为0.014~0.093 ng和0.016~0.026 ng,线性相关系数大于0.9975;用于3个城市PM10中的痕量多环芳烃和正构烷烃的定量测定,回收率分别在95%~135%(多环芳烃)和95%~115%(正构烷

  9. Hydrophilic interaction liquid chromatography with tandem mass spectrometric detection applied for analysis of pteridines in two Graphosoma species (Insecta: Heteroptera).

    Science.gov (United States)

    Kozlík, Petr; Krajíček, Jan; Kalíková, Květa; Tesařová, Eva; Cabala, Radomír; Exnerová, Alice; Stys, Pavel; Bosáková, Zuzana

    2013-07-01

    A new separation method involving hydrophilic interaction chromatography with tandem mass spectrometric detection has been developed for the analysis of pteridines, namely biopterin, isoxanthopterin, leucopterin, neopterin, xanthopterin and erythropterin in the cuticle of heteropteran insect species. Two columns, Atlantis HILIC Silica and ZIC(®)-HILIC were tested for the separation of these pteridines. The effect of organic modifier content, buffer type, concentration and pH in mobile phase on retention and separation behavior of the selected pteridines was studied and the separation mechanism was also investigated. The optimized conditions for the separation of pteridines consisted of ZIC(®)-HILIC column, mobile phase composed of acetonitrile/5mM ammonium acetate, pH 6.80, 85/15 (v/v), flow rate 0.5mL/min and column temperature 30°C. Detection was performed by tandem mass spectrometry operating in electrospray ionization with Agilent Jet Stream technology using the selected reaction monitoring mode. The optimized method provided a linearity range from 0.3 to 5000ng/mL (r>0.9975) and repeatability with relative standard deviation<8.09% for all the studied pteridines. The method was applied to the analysis of pteridines in the cuticle of larvae and three adult color forms of Graphosoma lineatum and one form of Graphosoma semipunctatum (Insecta: Hemiptera: Heteroptera: Pentatomidae). The analysis shows that different forms of Graphosoma species can be characterized by different distribution of individual pteridines, which affects the coloration of various forms. Only isoxanthopterin was found in all the five forms tested.

  10. The Bremen mass spectrometric facility for the measurement of helium isotopes, neon, and tritium in water.

    Science.gov (United States)

    Sültenfuss, Jürgen; Roether, Wolfgang; Rhein, Monika

    2009-06-01

    We describe the mass spectrometric facility for measuring helium isotopes, neon, and tritium that has been operative at this institute since 1989, and also the sampling and sample preparation steps that precede the mass spectrometric analysis. For water samples in a near-equilibrium with atmospheric air, the facility achieves precision for (3)He/(4)He ratios of+/-0.4% or better, and+/-0.8 % or better for helium and neon concentrations. Tritium precision is typically+/-3 % and the detection limit 10 mTU ( approximately 1.2.10(-3) Bq/kg of pure water). Sample throughputs can reach some thousands per year. These achievements are enabled, among other features, by automation of the measurement procedure and by elaborate calibration, assisted by continual development in detail. To date, we have measured more than 15,000 samples for tritium and 23,000 for helium isotopes and neon, mostly in the context of oceanographic and hydrologic work. Some results of such work are outlined. Even when atmospheric tritium concentrations have become rather uniform, tritium provides water ages if (3)He data are taken concurrently. The technique can resolve tritium concentrations in waters of the pre-nuclear era.

  11. Time-resolved visible/near-infrared spectrometric observations of the Galaxy 11 geostationary satellite

    Science.gov (United States)

    Bédard, Donald; Wade, Gregg A.

    2017-01-01

    Time-resolved spectrometric measurements of the Galaxy 11 geostationary satellite were collected on three consecutive nights in July 2014 with the 1.6-m telescope at the Observatoire du Mont-Mégantic in Québec, Canada. Approximately 300 low-resolution spectra (R ≈ 700 , where R = λ / Δλ) of the satellite were collected each night, covering a spectral range between 425 and 850 nm. The two objectives of the experiment were to conduct material-type identification from the spectra and to study how the spectral energy distribution inferred from these measurements varied as the illumination and observation geometry changed on nightly timescales. We present results that indicate the presence of a highly reflective aluminized surface corresponding to the solar concentrator arrays of the Galaxy 11 spacecraft. Although other material types could not be identified using the spectra, the results showed that the spectral energy distribution of the reflected sunlight from the Galaxy 11 spacecraft varied significantly, in a systematic manner, over each night of observation. The variations were quantified using colour indices calculated from the time-resolved spectrometric measurements.

  12. Ambient aerodynamic ionization source for remote analyte sampling and mass spectrometric analysis.

    Science.gov (United States)

    Dixon, R Brent; Sampson, Jason S; Hawkridge, Adam M; Muddiman, David C

    2008-07-01

    The use of aerodynamic devices in ambient ionization source development has become increasingly prevalent in the field of mass spectrometry. In this study, an air ejector has been constructed from inexpensive, commercially available components to incorporate an electrospray ionization emitter within the exhaust jet of the device. This novel aerodynamic device, herein termed remote analyte sampling, transport, and ionization relay (RASTIR) was used to remotely sample neutral species in the ambient and entrain them into an electrospray plume where they were subsequently ionized and detected using a linear ion trap Fourier transform mass spectrometer. Two sets of experiments were performed in the ambient environment to demonstrate the device's utility. The first involved the remote (approximately 1 ft) vacuum collection of pure sample particulates (i.e., dry powder) from a glass slide, entrainment and ionization at the ESI emitter, and mass spectrometric detection. The second experiment involved the capture (vacuum collection) of matrix-assisted laser desorbed proteins followed by entrainment in the ESI emitter plume, multiple charging, and mass spectrometric detection. This approach is in principle a RASTIR-assisted matrix-assisted laser desorption electrospray ionization source (Sampson, J. S.; Hawkridge, A. M.; Muddiman, D. C. J. Am. Soc. Mass Spectrom. 2006, 17, 1712-1716; Rapid Commun. Mass Spectrom. 2007, 21, 1150-1154.). A detailed description of the device construction, operational parameters, and preliminary small molecule and protein data are presented.

  13. Comprehensive mass spectrometric analysis of novel organic semiconductor molecules

    Science.gov (United States)

    Prada, Svitlana

    implemented. The contribution of the quadrupole RF field to the drift dynamics also was taken into consideration. The IMR was successfully employed in the ion-molecule reactions study of four functionalized pentacene derivatives such as TIPS, o-TIPS, 6,13-bis-[(triisopropylsilyl)-ethynyl]-pentacene-2,3-dicarbonitrile (TIPS(CN)2), and 6,13-bis-[(triisopropylsilyl)-ethynyl]-pentacene-2,3,9,10-tetracarbonitrile (TIPS(CN)4). Details of the IMR operation in this mode are extensively discussed. The purity of the starting material is one of the most important parameters for the fabrication of a molecular electronic device. We report the method of determination of trace elemental impurities (Li, Na, Al, Mg, Be, Pb, Mn, Co, Ti, Sn, Cu, Cr, V, Zn, Fe, Ca, K and Ni) in organic semiconductor materials, such as Tetracene, Anthracene, Pentacene, TIPS and Rubrene, using an inductively coupled plasma quadrupole mass spectrometer (ICP-MS) fitted with a dynamic reaction cell (DRC). The determination of Fe, Ca, K and Ni in the organic semiconductor materials was carried out using NH3 as a reaction gas in the DRC mode to obviate the effect of polyatomic isobaric interferences. The other trace elements such as Li, Na, Al, Mg, Be, Pb, Mn, Co, Ti, Sn, Cu, Cr, V and Zn have been determined under standard operating conditions.

  14. Determination of suvorexant in human plasma using 96-well liquid-liquid extraction and HPLC with tandem mass spectrometric detection.

    Science.gov (United States)

    Breidinger, S A; Simpson, R C; Mangin, E; Woolf, E J

    2015-10-01

    A method, using liquid chromatography with tandem mass spectrometric detection (LC-MS/MS), was developed for the determination of suvorexant (MK-4305, Belsomra(®)), a selective dual orexin receptor antagonist for the treatment insomnia, in human plasma over the concentration range of 1-1000ng/mL. Stable isotope labeled (13)C(2)H3-suvorexant was used as an internal standard. The sample preparation procedure utilized liquid-liquid extraction, in the 96-well format, of a 100μL plasma sample with methyl t-butyl ether. The compounds were chromatographed under isocratic conditions on a Waters dC18 (50×2.1mm, 3μm) column with a mobile phase consisting of 30/70 (v/v %) 10mM ammonium formate, pH3/acetonitrile at a flow rate of 0.3mL/min. Multiple reaction monitoring of the precursor-to-product ion pairs for suvorexant (m/z 451→186) and (13)C(2)H3-suvorexant (m/z 455→190) on an Applied Biosystems API 4000 tandem mass spectrometer was used for quantitation. Intraday assay precision, assessed in six different lots of control plasma, was within 10% CV at all concentrations, while assay accuracy ranged from 95.6 to 105.0% of nominal. Quality control (QC) samples in plasma were stored at -20°C. Initial within day analysis of QCs after one freeze-thaw cycle showed accuracy within 9.5% of nominal with precision (CV) of 6.7% or less. The plasma QC samples were demonstrated to be stable for up to 25 months at -20°C. The method described has been used to support clinical studies during Phase I through III of clinical development.

  15. Identifying tissue-specific signal variation in MALDI mass spectrometric imaging by use of an internal standard

    NARCIS (Netherlands)

    Pirman, D.A.; Kiss, A.; Heeren, R.M.A.; Yost, R.A.

    2013-01-01

    Generating analyte-specific distribution maps of compounds in a tissue sample by matrix-assisted laser desorption/ionization (MALDI) mass spectrometric imaging (MSI) has become a useful tool in numerous areas across the biological sciences. Direct analysis of the tissue sample provides MS images of

  16. Gas chromatography of organic microcontaminants using atomic emission and mass spectrometric detection combined in one instrument (GC-AED/MS)

    NARCIS (Netherlands)

    Mol, H.G.J.; Hankemeier, T.; Brinkman, U.A.T.

    1999-01-01

    This study describes the coupling of an atomic-emission detector and mass-spectrometric detector to a single gas chromatograph. Splitting of the column effluent enables simultaneous detection by atomic-emission detection (AED) and mass spectrometry (MS) and yields a powerful system for the target an

  17. First Results From the Gas Chromatograph Mass Spectrometer (GCMS) Experiment on the Cassini-Huygens Probe

    Science.gov (United States)

    Niemann, Hasso B.; Demick, J.; Haberman, J.; Harpold, D.; Kasprzak, W.; Raaen, E.; Way, S.; Atreya, S.; Carignan, G.; Bauer, S.

    2005-01-01

    The Huygens Probe of the Cassini Huygens Mission entered the atmosphere of the moon Titan on January 14,2005. The GCMS was part of the instrument complement on the Probe to measure in situ the chemical composition of the atmosphere during the probe descent and to support the Aerosol Collector Pyrolyser (ACP) experiment by serving as detector for the pyrolization products. The GCMS employed a quadrupole mass filter with a secondary electron multiplier detection system and a gas sampling system providing continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns. The mass spectrometer employed five electron impact ion sources with available electron energies of either 70 or 25 eV. Three ion sources served as detectors for the GC columns and two were dedicated to direct atmosphere sampling and ACP gas sampling, respectively. The GCMS gas inlet was heated to prevent condensation, and served to evaporate surface constituents after impact.

  18. Miniature Gas Chromatograph Mass Spectrometer for In-Situ Resource Utilization Project

    Data.gov (United States)

    National Aeronautics and Space Administration — In situ resource utilization (ISRU) is essential for several of NASA's future flagship missions. Currently envisioned ISRU plants include production of oxygen from...

  19. MOMA Gas Chromatograph-Mass Spectrometer onboard the 2018 ExoMars Mission: results and performance

    Science.gov (United States)

    Buch, A.; Pinnick, V. T.; Szopa, C.; Grand, N.; Humeau, O.; van Amerom, F. H.; Danell, R.; Freissinet, C.; Brinckerhoff, W.; Gonnsen, Z.; Mahaffy, P. R.; Coll, P.; Raulin, F.; Goesmann, F.

    2015-10-01

    The Mars Organic Molecule Analyzer (MOMA) is a dual ion source linear ion trap mass spectrometer that was designed for the 2018 joint ESA-Roscosmos mission to Mars. The main scientific aim of the mission is to search for signs of extant or extinct life in the near subsurface of Mars by acquiring samples from as deep as 2 m below the surface. MOMA will be a key analytical tool in providing chemical (molecular and chiral) information from the solid samples, with particular focus on the characterization of organic content. The MOMA instrument, itself, is a joint venture for NASA and ESA to develop a mass spectrometer capable of analyzing samples from pyrolysis/chemical derivatization gas chromatography (GC) as well as ambient pressure laser desorption ionization (LDI). The combination of the two analytical techniques allows for the chemical characterization of a broad range of compounds, including volatile and non-volatile species. Generally, MOMA can provide information on elemental and molecular makeup, polarity, chirality and isotopic patterns of analyte species. Here we report on the current performance of the MOMA prototype instruments, specifically the demonstration of the gas chromatographymass spectrometry (GC-MS) mode of operation.

  20. Performance of the MOMA Gas Chromatograph-Mass Spectrometer onboard the 2018 ExoMars Mission

    Science.gov (United States)

    Buch, Arnaud; Pinnick, Veronica; Szopa, Cyril; Grand, Noël; Freissinet, Caroline; Danell, Ryan; van Ameron, Friso; Arevalo, Ricardo; Brinckerhoff, William; Raulin, François; Mahaffy, Paul; Goesmann, Fred

    2015-04-01

    The Mars Organic Molecule Analyzer (MOMA) is a dual ion source linear ion trap mass spectrometer that was designed for the 2018 joint ESA-Roscosmos mission to Mars. The main scientific aim of the mission is to search for signs of extant or extinct life in the near subsurface of Mars by acquir-ing samples from as deep as 2 m below the surface. MOMA will be a key analytical tool in providing chemical (molecular) information from the solid samples, with particular focus on the characterization of organic content. The MOMA instrument, itself, is a joint venture for NASA and ESA to develop a mass spectrometer capable of analyzing samples from pyrolysis gas chromatograph (GC) as well as ambient pressure laser desorption ionization (LDI). The combination of the two analytical techniques allows for the chemical characterization of a broad range of compounds, including volatile and non-volatile species. Generally, MOMA can provide in-formation on elemental and molecular makeup, po-larity, chirality and isotopic patterns of analyte spe-cies. Here we report on the current performance of the MOMA prototype instruments, specifically the demonstration of the gas chromatography-mass spec-trometry (GC-MS) mode of operation. Both instruments have been tested separately first and have been coupled in order to test the efficiency of the future MOMA GC-MS instrument. The main objective of the second step has been to test the quantitative response of both instruments while they are coupled and to characterize the combined instrument detection limit for several compounds. A final experiment has been done in order to test the feasibility of the separation and detection of a mixture contained in a soil sample introduced in the MOMA oven.

  1. Biomarker distributions in asphaltenes and kerogens analyzed by flash pyrolysis-gas chromatograph-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Van Graas, G.

    1986-01-01

    Biomarker distributions in a suite of asphaltenes and kerogens have been analyzed by flash pyrolysis directly coupled to a GCMS system. Attention has been focussed on biomarkers of the sterane and triterpane types. The sample suite under investigation consists of sediments with different kerogen types and some crude oils. Biomarker distributions in the pyrolysates have been compared with the free biomarkers in the corresponding saturated hydrocarbon fractions. The analyses show significant differences between the distributions of the free biomarkers and those in the pyrolysates. The latter have lower amounts of steranes while diasteranes are absent or present at low concentrations only. In the triterpane traces a shift of maximum intensity from C/sub 30/ (free compounds) to C/sub 27//C/sub 29/ is observed. Furthermore, the pyrolysates contain a set of triterpanes that are present in the saturated hydrocarbon fractions. The observed differences between pyrolysates and free hydrocarbons can be explained partly by the processes occurring during pyrolysis such as bond rupture and subsequent stabilization of primary pyrolysis products. To a certain extent these differences also show that maturation processes occurring in sediments have effects on free biomarker molecules different from those on molecules that are enclosed in a macromolecular matrix (kerogen or asphaltenes). Differences between biomarker distributions of asphaltene and kerogen pyrolysates are relatively small. A comparison with the pyrolysates from extracted whole sediments suggests that these differences are mainly caused by interactions between the organic material and the mineral matrix during pyrolysis. Oil asphaltenes behave differently from sediment asphaltenes as their pyrolysates are more similar to the corresponding saturated hydrocarbon fractions, i.e. the differences described above are observed to a much smaller extent.

  2. Application of gamma ray spectrometric measurements and VLF-EM data for tracing vein type uranium mineralization

    Directory of Open Access Journals (Sweden)

    Ibrahim Gaafar

    2015-12-01

    Full Text Available This study is an attempt to use the gamma ray spectrometric measurements and VLF-EM data to identify the subsurface structure and map uranium mineralization along El Sela shear zone, South Eastern Desert of Egypt. Many injections more or less mineralized with uranium and associated with alteration processes were recorded in El Sela shear zone. As results from previous works, the emplacement of these injections is structurally controlled and well defined by large shear zones striking in an ENE–WSW direction and crosscut by NW–SE to NNW–SSE fault sets. VLF method has been applied to map the structure and the presence of radioactive minerals that have been delineated by the detection of high uranium mineralization. The electromagnetic survey was carried out to detect the presence of shallow and deep conductive zones that cross the granites along ENE–WSW fracturing directions and to map its spatial distribution. The survey comprised seventy N–S spectrometry and VLF-EM profiles with 20 m separation. The resulted data were displayed as composite maps for K, eU and eTh as well as VLF-Fraser map. Twelve profiles with 100 m separation were selected for detailed description. The VLF-EM data were interpreted qualitatively as well as quantitatively using the Fraser and the Karous–Hjelt filters. Fraser filtered data and relative current density pseudo-sections indicate the presence of shallow and deep conductive zones that cross the granites along ENE–WSW shearing directions. High uranium concentrations found just above the higher apparent current-density zones that coincide with El-Sela shear zone indicate a positive relation between conductivity and uranium minerals occurrence. This enables to infer that the anomalies detected by VLF-EM data are due to the highly conductive shear zone enriched with uranium mineralization extending for more than 80 m.

  3. Direct injection liquid chromatography/electrospray ionization mass spectrometric horse urine analysis for the quantification and confirmation of threshold substances for doping control. II. Determination of theobromine.

    Science.gov (United States)

    Vonaparti, A; Lyris, E; Panderi, I; Koupparis, M; Georgakopoulos, C

    2009-04-01

    In equine sport, theobromine is prohibited with a threshold level of 2 microg mL(-1) in urine, hence doping control laboratories have to establish quantitative and qualitative methods for its determination. Two simple liquid chromatography/mass spectrometry (LC/MS) methods for the identification and quantification of theobromine were developed and validated using the same sample preparation procedure but different mass spectrometric systems: ion trap mass spectrometry (ITMS) and time-of-flight mass spectrometry (TOFMS). Particle-free diluted urine samples were directly injected into the LC/MS systems, avoiding the time-consuming extraction step. 3-Propylxanthine was used as the internal standard. The tested linear range was 0.75-15 microg mL(-1). Matrix effects were evaluated analyzing calibration curves in water and different fortified horse urine samples. A great variation in the signal of theobromine and the internal standard was observed in different matrices. To overcome matrix effects, a standard additions calibration method was applied. The relative standard deviations of intra- and inter-day analysis were lower than 8.6 and 7.2%, respectively, for the LC/ITMS method and lower than 5.7 and 5.8%, respectively, for the LC/TOFMS method. The bias was less than 8.7% for both methods. The methods were applied to two case samples, demonstrating simplicity, accuracy and selectivity.

  4. A superheterodyne spectrometer for electronic paramagnetic. Resonance; Spectrometre superheterodyne de resonance paramagnetique electronique

    Energy Technology Data Exchange (ETDEWEB)

    Laffon, J.L. [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1963-12-15

    After a few generalities about electron paramagnetic resonance, a consideration of different experimental techniques authorises the choice of a particular type of apparatus. An EPR superheterodyne spectrometer built in the laboratory and having a novel circuit is described in detail. With this apparatus, many experimental results have been obtained and some of these are described as example. (author) [French] Apres quelques generalites sur le phenomene de resonance paramagnetique electronique, une synthese des differentes techniques experimentales, permet de fixer le choix d'un type d'appareillage. Un spectrometre de RPE superheterodyne realise en laboratoire et comportant un circuit original est expose dans le detail. Cet appareil a permis de nombreux resultats experimentaux dont quelques-uns sont decrits a titre d'exemple. (auteur)

  5. Mass spectrometric imaging of flavonoid glycosides and biflavonoids in Ginkgo biloba L.

    Science.gov (United States)

    Beck, Sebastian; Stengel, Julia

    2016-10-01

    Ginkgo biloba L. is known to be rich in flavonoids and flavonoid glycosides. However, the distribution within specific plant organs (e.g. within leaves) is not known. By using HPLC-MS and MS/MS we have identified a number of previously known G. biloba flavonoid glycosides and biflavonoids from leaves. Namely, kaempferol, quercetin, isorhamnetin, myricetin, laricitrin/mearnsetin and apigenin glycosides were identified. Furthermore, biflavonoids like ginkgetin/isoginkgetin were also detected. The application of MALDI mass spectrometric imaging, enabled the compilation of concentration profiles of flavonoid glycosides and biflavonoids in G. biloba L. leaves. Both, flavonoid glycosides and biflavonoids show a distinct distribution in leaf thin sections of G. biloba L.

  6. MASS SPECTROMETRIC ANALYSIS FOR THE IDENTIFICATION OF THUNNUS GENUS FOUR SPECIES

    Directory of Open Access Journals (Sweden)

    T. Pepe

    2011-01-01

    Full Text Available An accurate identification of similar fish species is necessary to prevent illegal substitution and is imposed by labeling regulations in UE countries (1. The genus Thunnus comprises many species of different quality and commercial value. The increasing trade of fish preparations of the species included in this genus and the consequent loss of the external anatomical and morphological features enables fraudulent substitutions. This study reports data relating to the proteomic analysis of four tuna species (T. thynnus, T. alalunga, T. albacares, T. obesus. Sarcoplasmic proteins were studied by mono and two dimensional electrophoresis. The most significant proteins for the characterization of the species were analyzed by mass spectrometric techniques. As reported in a previous study (2, an accurate identification of the species seems possible, owing to the polymorphism displayed by the species of the Thunnus genus.

  7. Proteogenomics meets cancer immunology: mass spectrometric discovery and analysis of neoantigens.

    Science.gov (United States)

    Polyakova, Anna; Kuznetsova, Ksenia; Moshkovskii, Sergei

    2015-01-01

    Cancer proteogenomics is an emerging field that aims to identify and quantify protein sequence changes associated with the cancer genome. Besides being involved in cancer development and progression, such protein variants may serve as neoantigens, which provide the T-cell response against tumors. Mass spectrometry-based proteogenomics may be a promising tool for finding neoantigens in individual specimens. It is partly based on a technical background accumulated from mass spectrometric studies of peptide ligands of major histocompatibility complex proteins. Examples of the use of mass spectrometry in neoantigen identification are reviewed in this article. Some experimental workflows are discussed, which may use shotgun and targeted proteomics for translational human studies of neoepitopes, such as cancer vaccine development and checkpoint therapy response prediction.

  8. Laser Spectrometric Measurement System for Local Express Diagnostics of Flame at Combustion of Liquid Hydrocarbon Fuels

    Science.gov (United States)

    Kobtsev, V. D.; Kozlov, D. N.; Kostritsa, S. A.; Smirnov, V. V.; Stel'makh, O. M.; Tumanov, A. A.

    2016-03-01

    A laboratory laser spectrometric measurement system for investigation of spatial distributions of local temperatures in a flame at combustion of vapors of various liquid hydrocarbon fuels in oxygen or air at atmospheric pressure is presented. The system incorporates a coherent anti-Stokes Raman spectrometer with high spatial resolution for local thermometry of nitrogen-containing gas mixtures in a single laser shot and a continuous operation burner with a laminar diffusion flame. The system test results are presented for measurements of spatial distributions of local temperatures in various flame zones at combustion of vapor—gas n-decane/nitrogen mixtures in air. Its applicability for accomplishing practical tasks in comparative laboratory investigation of characteristics of various fuels and for research on combustion in turbulent flames is discussed.

  9. Regime transition in electromechanical fluid atomization and implications to analyte ionization for mass spectrometric analysis.

    Science.gov (United States)

    Forbes, Thomas P; Degertekin, F Levent; Fedorov, Andrei G

    2010-11-01

    The physical processes governing the transition from purely mechanical ejection to electromechanical ejection to electrospraying are investigated through complementary scaling analysis and optical visualization. Experimental characterization and visualization are performed with the ultrasonically-driven array of micromachined ultrasonic electrospray (AMUSE) ion source to decouple the electrical and mechanical fields. A new dimensionless parameter, the Fenn number, is introduced to define a transition between the spray regimes, in terms of its dependence on the characteristic Strouhal number for the ejection process. A fundamental relationship between the Fenn and Strouhal numbers is theoretically derived and confirmed experimentally in spraying liquid electrolytes of different ionic strength subjected to a varying magnitude electric field. This relationship and the basic understanding of the charged droplet generation physics have direct implications on the optimal ionization efficiency and mass spectrometric response for different types of analytes.

  10. Determination of Mass Spectrometric Sensitivity of Different Metalloporphyrin Esters Relative to Porphyrin Ester

    DEFF Research Database (Denmark)

    Larsen, Elfinn; Egsgaard, Helge; Møller, J.

    1977-01-01

    Quantitative determination of metalloporphyrin contamination in preparations of biologically important porphyrins was achieved mass spectrometrically by application of the integrated ion current technique. For this purpose, the relative molecular ion sensitivities of the contaminating metal compl...... complexes were determined from the ratios of the integrated molecular ion currents of a series of calibration samples containing a porphyrin ester and one of its metal complexes in known molar ratio. Complexes formed with divalent ions of Cu, Zn, Fe, Co and Ni of copro- as well as uro......-prophyrin permethylester were all found to have the same molecular ion sensitivities as their metal-free porphyrin ester. The relative metalloporphyrin ester content in a sample of porphyrin ester was thus obtained directly as the integrated ion current ratios of the normalized molecular ions. The preparation...

  11. Mass Spectrometric Calibration of Controlled Fluoroform Leak Rate Devices Technique and Uncertainty Analysis

    CERN Document Server

    Balsley, S D; Laduca, C A

    2003-01-01

    Controlled leak rate devices of fluoroform on the order of 10 sup - sup 8 atm centre dot cc sec sup - sup 1 at 25 C are used to calibrate QC-1 War Reserve neutron tube exhaust stations for leak detection sensitivity. Close-out calibration of these tritium-contaminated devices is provided by the Gas Dynamics and Mass Spectrometry Laboratory, Organization 14406, which is a tritium analytical facility. The mass spectrometric technique used for the measurement is discussed, as is the first principals calculation (pressure, volume, temperature and time). The uncertainty of the measurement is largely driven by contributing factors in the determination of P, V and T. The expanded uncertainty of the leak rate measurement is shown to be 4.42%, with a coverage factor of 3 (k=3).

  12. GNU polyxmass: a software framework for mass spectrometric simulations of linear (bio-polymeric analytes

    Directory of Open Access Journals (Sweden)

    Rusconi Filippo

    2006-04-01

    Full Text Available Abstract Background Nowadays, a variety of (bio-polymers can be analyzed by mass spectrometry. The detailed interpretation of the spectra requires a huge number of "hypothesis cycles", comprising the following three actions 1 put forth a structural hypothesis, 2 test it, 3 (invalidate it. This time-consuming and painstaking data scrutiny is alleviated by using specialized software tools. However, all the software tools available to date are polymer chemistry-specific. This imposes a heavy overhead to researchers who do mass spectrometry on a variety of (bio-polymers, as each polymer type will require a different software tool to perform data simulations and analyses. We developed a software to address the lack of an integrated software framework able to deal with different polymer chemistries. Results The GNU polyxmass software framework performs common (bio-chemical simulations–along with simultaneous mass spectrometric calculations–for any kind of linear bio-polymeric analyte (DNA, RNA, saccharides or proteins. The framework is organized into three modules, all accessible from one single binary program. The modules let the user to 1 define brand new polymer chemistries, 2 perform quick mass calculations using a desktop calculator paradigm, 3 graphically edit polymer sequences and perform (bio-chemical/mass spectrometric simulations. Any aspect of the mass calculations, polymer chemistry reactions or graphical polymer sequence editing is configurable. Conclusion The scientist who uses mass spectrometry to characterize (bio-polymeric analytes of different chemistries is provided with a single software framework for his data prediction/analysis needs, whatever the polymer chemistry being involved.

  13. Absorption spectrum, mass spectrometric properties, and electronic structure of 1,2-benzoquinone.

    Science.gov (United States)

    Albarran, Guadalupe; Boggess, William; Rassolov, Vitaly; Schuler, Robert H

    2010-07-22

    Absorption spectrophotometric and mass spectrometric properties of 1,2-benzoquinone, prepared in aqueous solution by the hexachloroiridate(IV) oxidation of catechol and isolated by HPLC, are reported. Its absorption spectrum has a broad moderately intense band in the near UV with an extinction coefficient of 1370 M(-1)cm(-1) at its 389 nm maximum. The oscillator strength of this band contrasts with those of the order-of-magnitude stronger approximately 250 nm bands of most 1,4-benzoquinones. Gaussian analysis of its absorption spectrum indicates that it also has modestly intense higher energy bands in the 250-320 nm region. In atmospheric pressure mass spectrometric studies 1,2-benzoquinone exhibits very strong positive and negative mass 109 signals that result from the addition of protons and hydride ions in APCI and ESI ion sources. It is suggested that the hydride adduct is formed as the result of the highly polar character of ortho-quinone. On energetic collision the hydride adduct loses an H atom to produce the 1,2-benzosemiquinone radical anion. The present studies also show that atmospheric pressure mass spectral patterns observed for catechol are dominated by signals of 1,2-benzoquinone resulting from oxidation of catechol in the ion sources. Computational studies of the electronic structures of 1,2-benzoquinone, its proton and hydride ion adducts, and 1,2-benzosemiquinone radical anion are reported. These computational studies show that the structures of the proton and hydride adducts are similar and indicate that the hydride adduct is the proton adduct of a doubly negatively charged 1,2-benzoquinone. The contrast between the properties of 1,2- and 1,4-benzoquinone provides the basis for considerations on the effects of conjugation in aromatic systems.

  14. Application of comprehensive two-dimensional gas chromatography with mass spectrometric detection for the analysis of selected drug residues in wastewater and surface water

    Institute of Scientific and Technical Information of China (English)

    Petr Lacina; Ludmila Mravcová; Milada Vávrová

    2013-01-01

    Pharmaceutical residues have become tightly controlled environmental contaminants in recent years,due to their increasing concentration in environmental components.This is mainly caused by their high level of production and everyday consumption.Therefore there is a need to apply new and sufficiently sensitive analytical methods,which can detect the presence of these contaminants even in very low concentrations.This study is focused on the application of a reliable analytical method for the analysis of 10 selected drug residues,mainly from the group of non-steroidal anti-iaffammatory drugs (salicylic acid,acetylsalicylic acid,clofibric acid,ibuprofen,acetaminophen,caffeine,naproxen,mefenamic acid,ketoprofen,and dicofenac),in wastewaters and surface waters.This analytical method is based on solid phase extraction,derivatization by N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) and finally analysis by comprehensive two-dimensional gas chromatography with Time-of-Flight mass spectrometric detection (GCxGC-TOF MS).Detection limits ranged from 0.18 to 5 ng/L depending on the compound and selected matrix.The method was successfully applied for detection of the presence of selected pharmaceuticals in the Svratka River and in wastewater from the wastewater treatment plant in Brno-Modrice,Czech Republic.The concentration of pharmaceuticals varied from one to several hundreds of ng/L in surface water and from one to several tens of μg/L in wastewater.

  15. Mass spectrometric identification of an azobenzene derivative produced by smectite-catalyzed conversion of 3-amino-4-hydroxyphenylarsonic acid

    Science.gov (United States)

    Wershaw, R. L.; Rutherford, D.W.; Rostad, C.E.; Garbarino, J.R.; Ferrer, I.; Kennedy, K.R.; Momplaisir, G.-M.; Grange, A.

    2003-01-01

    The compound 3-amino-4-hydroxyphenylarsonic acid (3-amino-HPAA) reacts with smectite to form a soluble azobenzene arsonic acid compound. This reaction is of particular interest because it provides a possible mechanism for the formation of a new type of arsenic compound in natural water systems. 3-Amino-HPAA is a degradation product excreted by chickens that are fed rations amended with roxarsone. Roxarsone is used to control coccidial intestinal parasites in most of the broiler chickens grown in the United States. The structure of the azobenzene arsonic acid compound was first inferred from negative-ion and positive-ion low-resolution mass-spectrometric analyses of the supernatant of the smectite suspension. Elemental composition of the parent ion determined by high-resolution positive-ion mass spectrometric measurements was consistent with the proposed structure of the azobenzene arsonic acid compound. Published by Elsevier Science B.V.

  16. Nuclear Forensic Materials and Methods

    Science.gov (United States)

    Hutcheon, I. D.; Grant, P. M.; Moody, K. J.

    A short history and treatment of the various aspects of nuclear forensic analysis is followed by a discussion of the most common chemical procedures, including applications of tracers, radioisotopic generators, and sample chronometry. Analytic methodology discussed includes sample preparation, radiation detection, various forms of microscopy, and mass-spectrometric techniques. The chapter concludes with methods for the production and treatment of special nuclear materials and with a description of several actual case studies conducted at Livermore.

  17. Analysis methods for airborne radioactivity

    OpenAIRE

    Ala-Heikkilä, Jarmo J

    2008-01-01

    High-resolution gamma-ray spectrometry is an analysis method well suitable for monitoring airborne radioactivity. Many of the natural radionuclides and a majority of anthropogenic nuclides are prominent gamma-ray emitters. With gamma-ray spectrometry different radionuclides are readily observed at minute concentrations that are far from health hazards. The gamma-ray spectrometric analyses applied in air monitoring programmes can be divided into particulate measurements and gas measurements. I...

  18. Relationships between ground and airborne gamma-ray spectrometric survey data, North Ras Millan, Southern Sinai Peninsula, Egypt.

    Science.gov (United States)

    Youssef, Mohamed A S

    2016-02-01

    In the last decades of years, there was considerable growth in the use of airborne gamma-ray spectrometry. With this growth, there was an increasing need to standardize airborne measurements, so that they can be independent of survey parameters. Acceptable procedures were developed for converting airborne to ground gamma-ray spectrometric measurements of total-count intensity as well as, potassium, equivalent uranium and equivalent thorium concentrations, due to natural sources of radiation. The present study aims mainly to establish relationships between ground and airborne gamma-ray spectrometric data, North Ras Millan, Southern Sinai Peninsula, Egypt. The relationships between airborne and ground gamma-ray spectrometric data were deduced for the original and separated rock units in the study area. Various rocks in the study area, represented by Quaternary Wadi sediments, Cambro-Ordovician sandstones, basic dykes and granites, are shown on the detailed geologic map. The structures are displayed, which located on the detailed geologic map, are compiled from the integration of previous geophysical and surface geological studies.

  19. Identification and determination of phase II nabumetone metabolites by high-performance liquid chromatography with photodiode array and mass spectrometric detection.

    Science.gov (United States)

    Nobilis, M; Holcapek, M; Kolárová, L; Kopecký, J; Kunes, M; Svoboda, Z; Kvetina, J

    2004-03-26

    Chromatographic analyses play an important role in the identification and determination of phase I and phase II drug metabolites. While the chemical standards of phase I metabolites are usually available from commercial sources or by various synthetic, degradation or isolation methods, the phase II drug metabolites have usually more complicated structures, their standards are in general inaccessible and their identification and determination require a comprehensive analytical approach involving the use of xenobiochemical methods and the employment of hyphenated analytical techniques. In this work, various high-performance liquid chromatography (HPLC) methods were employed in the evaluation of xenobiochemical experiments leading to the identification and determination of phase II nabumetone metabolites. Optimal conditions for the quantitative enzymatic deconjugation of phase II metabolites were found for the samples of minipig bile, small intestine contents and urine. Comparative HPLC analyses of the samples of above-mentioned biomatrices and of the same biomatrices after their enzymatic treatment using beta-glucuronidase and arylsulfatase afforded the qualitative and quantitative information about phase II nabumetone metabolites. Hereby, three principal phase II nabumetone metabolites (ether glucuronides) were discovered in minipig's body fluids and their structures were confirmed using liquid chromatography (LC)-electrospray ionization mass spectrometric (MS) analyses.

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

    Science.gov (United States)

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

    2016-09-01

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

  1. Simple and sensitive determination of o-phenylphenol in citrus fruits using gas chromatography with atomic emission or mass spectrometric detection.

    Science.gov (United States)

    Kolbe, Nina; Andersson, Jan T

    2006-08-09

    In this work, a simple and sensitive method for the analysis of the pesticide o-phenylphenol (OPP) on citrus fruits was developed. OPP is extracted with dichloromethane by ultrasonication and derivatized with ferrocenecarboxylic acid chloride. Using ferrocene as a label, residues of OPP are determined by gas chromatography with atomic emission detection in the iron selective mode or with mass spectrometric detection. Sample cleanup is simple and rapid and merely involves a removal of excess reagent on an alumina minicolumn. The method detection limit is 2 ng of OPP/g of fruit, and recoveries from lemon samples fortified at levels of 35 and 140 ng/g are 101 and 106%, respectively. The citrus fruits analyzed (oranges, grapefruits, lemons) contained between 60 ng/g and 0.37 microg/g OPP (RSD = 8-13%), and the results were in good agreement with results obtained when OPP was analyzed using an established HPLC-FLD method. Several alcohols could also be identified in the fruit peel.

  2. Determination of plutonium isotopes (238Pu, 239Pu, 240Pu, 241Pu) in environmental samples using radiochemical separation combined with radiometric and mass spectrometric measurements.

    Science.gov (United States)

    Xu, Yihong; Qiao, Jixin; Hou, Xiaolin; Pan, Shaoming; Roos, Per

    2014-02-01

    This paper reports an analytical method for the determination of plutonium isotopes ((238)Pu, (239)Pu, (240)Pu, (241)Pu) in environmental samples using anion exchange chromatography in combination with extraction chromatography for chemical separation of Pu. Both radiometric methods (liquid scintillation counting and alpha spectrometry) and inductively coupled plasma mass spectrometry (ICP-MS) were applied for the measurement of plutonium isotopes. The decontamination factors for uranium were significantly improved up to 7.5 × 10(5) for 20 g soil compared to the level reported in the literature, this is critical for the measurement of plutonium isotopes using mass spectrometric technique. Although the chemical yield of Pu in the entire procedure is about 55%, the analytical results of IAEA soil 6 and IAEA-367 in this work are in a good agreement with the values reported in the literature or reference values, revealing that the developed method for plutonium determination in environmental samples is reliable. The measurement results of (239+240)Pu by alpha spectrometry agreed very well with the sum of (239)Pu and (240)Pu measured by ICP-MS. ICP-MS can not only measure (239)Pu and (240)Pu separately but also (241)Pu. However, it is impossible to measure (238)Pu using ICP-MS in environmental samples even a decontamination factor as high as 10(6) for uranium was obtained by chemical separation.

  3. Mass spectrometric survey of peptides in cephalopods with an emphasis on the FMRFamide-related peptides.

    Science.gov (United States)

    Sweedler, J V; Li, L; Floyd, P; Gilly, W

    2000-12-01

    A matrix-assisted laser desorption/ionization (MALDI) mass spectrometric (MS) survey of the major peptides in the stellar, fin and pallial nerves and the posterior chromatophore lobe of the cephalopods Sepia officinalis, Loligo opalescens and Dosidicus gigas has been performed. Although a large number of putative peptides are distinct among the three species, several molecular masses are conserved. In addition to peptides, characterization of the lipid content of the nerves is reported, and these lipid peaks account for many of the lower molecular masses observed. One conserved set of peaks corresponds to the FMRFamide-related peptides (FRPs). The Loligo opalescens FMRFa gene has been sequenced. It encodes a 331 amino acid residue prohormone that is processed into 14 FRPs, which are both predicted by the nucleotide sequence and confirmed by MALDI MS. The FRPs predicted by this gene (FMRFa, FLRFa/FIRFa and ALSGDAFLRFa) are observed in all three species, indicating that members of this peptide family are highly conserved across cephalopods.

  4. Measuring masses of large biomolecules and bioparticles using mass spectrometric techniques.

    Science.gov (United States)

    Peng, Wen-Ping; Chou, Szu-Wei; Patil, Avinash A

    2014-07-21

    Large biomolecules and bioparticles play a vital role in biology, chemistry, biomedical science and physics. Mass is a critical parameter for the characterization of large biomolecules and bioparticles. To achieve mass analysis, choosing a suitable ion source is the first step and the instruments for detecting ions, mass analyzers and detectors should also be considered. Abundant mass spectrometric techniques have been proposed to determine the masses of large biomolecules and bioparticles and these techniques can be divided into two categories. The first category measures the mass (or size) of intact particles, including single particle quadrupole ion trap mass spectrometry, cell mass spectrometry, charge detection mass spectrometry and differential mobility mass analysis; the second category aims to measure the mass and tandem mass of biomolecular ions, including quadrupole ion trap mass spectrometry, time-of-flight mass spectrometry, quadrupole orthogonal time-of-flight mass spectrometry and orbitrap mass spectrometry. Moreover, algorithms for the mass and stoichiometry assignment of electrospray mass spectra are developed to obtain accurate structure information and subunit combinations.

  5. Thermoluminescence (TL) spectra from quartz grains using on-line TL-spectrometric system

    Energy Technology Data Exchange (ETDEWEB)

    Hashimoto, T.; Sugai, N.; Sakaue, H.; Shirai, N. [Niigata University, Niigata (Japan). Faculty of Science; Yasuda, K. [Daiwa Geological Laboratory Co. Ltd., Fukushima (Japan)

    1997-12-31

    An on-line spectrometric system installed with a small spectrometer and an image intensifier unit has been developed for weak and changeable TL-spectrum measurements with rising temperature for application to natural minerals. The detection sensitivity over visible wavelength regions was corrected using a known spectrum from a standard light source, and the detection sensitivity was also examined by a chemical luminol reaction. In an applied experiment, two quartz grain samples from two pyroclastic flows of the same origin, were subjected to testing with the present measuring system. The original data, consisting of 512 channels for every second at a constant heating rate of 1degC/s, were used to create a contour map or a 3-dimensional expression of TL-spectra after subtraction of background radiation. The artificially irradiated quartz grains clearly showed both red (RTL) and blue TL (BTL) in contrast to RTL alone from naturally accumulated TL. Both spectral expressions and glow curves from the same original data were found to be available to estimate quartz formation temperatures, together with thermoluminescence color images (TLCIs). 24 refs., 9 figs.

  6. Precise timing of the last interglacial period from mass spectrometric determination of thorium-230 in corals

    Science.gov (United States)

    Chen, J. H.; Wasserburg, G. J.; Ku, T.-L.; Edwards, R. Lawrence

    1987-01-01

    The development of mass spectrometric techniques for determination of Th-230 abundance has made it possible to reduce analytical errors in (U-238)-(U-234)-(Th-230) dating of corals even with very small samples. Samples of 6 x 10 to the 8th atoms of Th-230 can be measured to an accuracy of + or - 3 percent (2sigma), and 3 x 10 to the 10th atoms of Th-230 can be measured to an accuracy of + or - 0.2 percent. The time range over which useful age data on corals can be obtained now ranges from about 50 to about 500,000 years. For young corals, this approach may be preferable to C-14 dating. The precision with which the age of a coral can now be determined should make it possible to critically test the Milankovitch hypothesis concerning Pleistocene climate fluctuations. Analyses of a number of corals that grew during the last interglacial period yield ages of 122,000 to 130,000 years. The ages coincide with, or slightly post-date, the summer solar insolation high at 65 deg N latitude which occurred 128,000 years ago. This supports the idea that changes in Pleistocene climate can be the result of variations in the distribution of solar insolation caused by changes in the geometry of the earth's orbit and rotation axis.

  7. Evaluation of airborne gamma-ray spectrometric data for the Missikat uranium deposit, Eastern Desert, Egypt.

    Science.gov (United States)

    Abd El Nabi, S H

    2001-03-01

    The examination of gamma-ray spectrometric data of the Missikat area was found to be useful in locating areas worth exploring for uranium occurrence. The statistical treatment of these data shows that the uranium threshold level is 13 ppm. Such a value represents indirectly the presence of uranium mineralization and identifies anomalous areas on the eU contour map in the northern border of the Missikat-Ria El Gerra granitic plutons. This area should be of prime concern in uranium exploration of these plutons. The interpretation of the variation in the eU/eTh ratio with eU and eTh suggests that uranium redistribution has occurred within the Missikat-Ria El Gerra granitic plutons. Uranium may be reconcentrated in silicification, sericitization and kaolinization alterations which are geologically evident. eU, eTh and their ratio eU/eTh for the Missikat-Ria El Gerra granites exhibit a lognormal distribution which is in agreement with the general distribution of trace elements, whereas the K content tends towards a normal distribution.

  8. Gamma-spectrometric module based on HPGe detector for radiation portal monitors

    Directory of Open Access Journals (Sweden)

    Kondratjev Vladimir

    2015-01-01

    Full Text Available The appearance of small-sized and powerful enough electric cryocoolers of various types on the market, has opened the perspective of HPGe detectors application, cooled by such coolers, in radiation portal monitors. The first results of a spectrometric module based on HPGe detector with relative efficiency of 45% cooled by a Stirling-cycle cryocooler, are presented. The spectrometer has provided energy resolutions of less than 0.95 keV and 1.95 keV at energies of 122 keV and 1332 keV, respectively. The deterioration of the energy resolution of HPGe detector cooled by electric cryocooler in comparison to the resolution with liquid nitrogen cooling was about 8% at the energy of 1332 keV. With the use of activated filters to suppress pulses produced by the mechanical vibrations, the energy resolution of the spectrometer was 0.8 keV and 1.8 keV, respectively, however, the detector relative efficiency at the energy of 1332 keV has dropped to 39 %.

  9. Vapor generation – atomic spectrometric techniques. Expanding frontiers through specific-species preconcentration. A review

    Energy Technology Data Exchange (ETDEWEB)

    Gil, Raúl A.; Pacheco, Pablo H.; Cerutti, Soledad [Área de Química Analítica, Facultad de Química Bioquímica y Farmacia, Universidad Nacional de San Luis, Ciudad de San Luis 5700 (Argentina); Instituto de Química de San Luis, INQUISAL, Centro Científico-Tecnológico de San Luis (CCT-San Luis), Consejo Nacional de Investigaciones Científicas y Universidad Nacional de San Luis, Ciudad de San Luis 5700 (Argentina); Martinez, Luis D., E-mail: ldm@unsl.edu.ar [Área de Química Analítica, Facultad de Química Bioquímica y Farmacia, Universidad Nacional de San Luis, Ciudad de San Luis 5700 (Argentina); Instituto de Química de San Luis, INQUISAL, Centro Científico-Tecnológico de San Luis (CCT-San Luis), Consejo Nacional de Investigaciones Científicas y Universidad Nacional de San Luis, Ciudad de San Luis 5700 (Argentina)

    2015-05-22

    This article reviews 120 articles found in SCOPUS and specific Journal cites corresponding to the terms ‘preconcentration’; ‘speciation’; ‘vapor generation techniques’ and ‘atomic spectrometry techniques’ in the last 5 years. - Highlights: • Recent advances in vapor generation and atomic spectrometry were reviewed. • Species-specific preconcentration strategies after and before VG were discussed. • New preconcentration and speciation analysis were evaluated within this framework. - Abstract: We review recent progress in preconcentration strategies associated to vapor generation techniques coupled to atomic spectrometric (VGT-AS) for specific chemical species detection. This discussion focuses on the central role of different preconcentration approaches, both before and after VG process. The former was based on the classical solid phase and liquid–liquid extraction procedures which, aided by automation and miniaturization strategies, have strengthened the role of VGT-AS in several research fields including environmental, clinical, and others. We then examine some of the new vapor trapping strategies (atom-trapping, hydride trapping, cryotrapping) that entail improvements in selectivity through interference elimination, but also they allow reaching ultra-low detection limits for a large number of chemical species generated in conventional VG systems, including complete separation of several species of the same element. This review covers more than 100 bibliographic references from 2009 up to date, found in SCOPUS database and in individual searches in specific journals. We finally conclude by giving some outlook on future directions of this field.

  10. Mass Spectrometric Imaging of Red Fluorescent Protein in Breast Tumor Xenografts

    Science.gov (United States)

    Chughtai, Kamila; Jiang, Lu; Post, Harm; Winnard, Paul T.; Greenwood, Tiffany R.; Raman, Venu; Bhujwalla, Zaver M.; Heeren, Ron M. A.; Glunde, Kristine

    2013-05-01

    Mass spectrometric imaging (MSI) in combination with electrospray mass spectrometry (ESI-MS) is a powerful technique for visualization and identification of a variety of different biomolecules directly from thin tissue sections. As commonly used tools for molecular reporting, fluorescent proteins are molecular reporter tools that have enabled the elucidation of a multitude of biological pathways and processes. To combine these two approaches, we have performed targeted MS analysis and MALDI-MSI visualization of a tandem dimer (td)Tomato red fluorescent protein, which was expressed exclusively in the hypoxic regions of a breast tumor xenograft model. For the first time, a fluorescent protein has been visualized by both optical microscopy and MALDI-MSI. Visualization of tdTomato by MALDI-MSI directly from breast tumor tissue sections will allow us to simultaneously detect and subsequently identify novel molecules present in hypoxic regions of the tumor. MS and MALDI-MSI of fluorescent proteins, as exemplified in our study, is useful for studies in which the advantages of MS and MSI will benefit from the combination with molecular approaches that use fluorescent proteins as reporters.

  11. Simple field-based automated dispersive liquid-liquid microextraction of trace level phthalate esters in natural waters with gas chromatography and mass spectrometric analysis.

    Science.gov (United States)

    Leng, Geng; Chen, Wenjin; Wang, Yong

    2016-09-01

    A small, simple, and field-based automated dispersive liquid-liquid microextraction method followed by gas chromatography mass spectrometric analysis was developed for trace level phthalate esters analysis in natural waters. With a single syringe pump that is coupled with a multiposition valve, the whole extraction procedure including cleaning, sampling, mixing of extractant and disperser solvents, extraction, phase separation, and analytes collection was carried out in a totally automated way with a sample throughput of 21 h(-1) . Key factors, such as type and ratio of the extractant and disperser solvent, aspiration flow rate, extraction time, and matrix effect, were thoroughly investigated. Under the optimum conditions, linearity was found in the range from 0.03 to 60 μg/L. Limits of detection ranged from 0.0015 to 0.003 μg/L. Enrichment factors were in a range of 106-141. Reproducibility and recoveries were assessed by testing a series of three natural water samples that were spiked with different concentration levels. Finally, the proposed method was successfully applied in analysis of real surface waters. The developed system is inexpensive, light (2.6 kg), simple to use, applicable in the field, with high sample throughput, and sensitive enough for trace level phthalate esters analysis in natural waters.

  12. A Simple and Effective Mass Spectrometric Approach to Identify the Adulteration of the Mediterranean Diet Component Extra-Virgin Olive Oil with Corn Oil

    Directory of Open Access Journals (Sweden)

    Francesco Di Girolamo

    2015-09-01

    Full Text Available Extra virgin olive oil (EVOO with its nutraceutical characteristics substantially contributes as a major nutrient to the health benefit of the Mediterranean diet. Unfortunately, the adulteration of EVOO with less expensive oils (e.g., peanut and corn oils, has become one of the biggest source of agricultural fraud in the European Union, with important health implications for consumers, mainly due to the introduction of seed oil-derived allergens causing, especially in children, severe food allergy phenomena. In this regard, revealing adulterations of EVOO is of fundamental importance for health care and prevention reasons, especially in children. To this aim, effective analytical methods to assess EVOO purity are necessary. Here, we propose a simple, rapid, robust and very sensitive method for non-specialized mass spectrometric laboratory, based on the matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOF MS coupled to unsupervised hierarchical clustering (UHC, principal component (PCA and Pearson’s correlation analyses, to reveal corn oil (CO adulterations in EVOO at very low levels (down to 0.5%.

  13. Identification of Polish cochineal (Porphyrophora polonica L.) in historical textiles by high-performance liquid chromatography coupled with spectrophotometric and tandem mass spectrometric detection.

    Science.gov (United States)

    Lech, Katarzyna; Jarosz, Maciej

    2016-05-01

    The present work reports a method for identification of Polish cochineal (Porphyrophora polonica L.) in historical fabrics by the use of high-performance liquid chromatography coupled with diode array and tandem mass spectrometric detection with electrospray ionization (HPLC-DAD-ESI MS/MS). This hyphened technique allows detection and identification of 16 new minor colorants present in the discussed scale insect (including two previously observed by Wouters and Verhecken (Ann Soc Entomol Fr. 1989;25:393-410), but specified only as compounds of unknown structures) that do not occur (e.g., in American cochineal). The MS/MS experiments, complemented with UV-VIS data, enable identification of mono- and di-, C- and O-hexosides of kermesic and flavokermesic acids or their derivatives. The present paper introduces a fingerprint of color compounds present in Polish cochineal and defines them, particularly pp6 (ppI, O-hexoside of flavokermesic acid), as its markers allow distinguishing of Polish-cochineal reds from the American ones. Usefulness of the selected set of markers for identification of Polish cochineal has been demonstrated in the examination of textiles from the collection of the National Museum in Warsaw using the multiple reaction monitoring (MRM) method, originally elaborated on the basis of this study.

  14. A Simple and Effective Mass Spectrometric Approach to Identify the Adulteration of the Mediterranean Diet Component Extra-Virgin Olive Oil with Corn Oil.

    Science.gov (United States)

    Di Girolamo, Francesco; Masotti, Andrea; Lante, Isabella; Scapaticci, Margherita; Calvano, Cosima Damiana; Zambonin, Carlo; Muraca, Maurizio; Putignani, Lorenza

    2015-09-01

    Extra virgin olive oil (EVOO) with its nutraceutical characteristics substantially contributes as a major nutrient to the health benefit of the Mediterranean diet. Unfortunately, the adulteration of EVOO with less expensive oils (e.g., peanut and corn oils), has become one of the biggest source of agricultural fraud in the European Union, with important health implications for consumers, mainly due to the introduction of seed oil-derived allergens causing, especially in children, severe food allergy phenomena. In this regard, revealing adulterations of EVOO is of fundamental importance for health care and prevention reasons, especially in children. To this aim, effective analytical methods to assess EVOO purity are necessary. Here, we propose a simple, rapid, robust and very sensitive method for non-specialized mass spectrometric laboratory, based on the matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOF MS) coupled to unsupervised hierarchical clustering (UHC), principal component (PCA) and Pearson's correlation analyses, to reveal corn oil (CO) adulterations in EVOO at very low levels (down to 0.5%).

  15. Laser ablation inductively coupled plasma mass spectrometric analyses of base metals in arctic char (Salvelinus alpinus) otoliths collected from a flooded base metal mine.

    Science.gov (United States)

    Friedrich, Lisa A; Halden, Norman M

    2011-05-15

    Otoliths from arctic char recovered from the water body formed from an abandoned open-pit nickel-copper mine contain a trace element record related to the geology of the immediate watershed, past mining activity in the area, and the fish's diet. Laser ablation inductively coupled plasma mass spectrometric analyses across the annular structure of the otoliths detected trace amounts of nickel, copper, and chromium believed to be related to the metal-bearing, mafic-ultramafic minerals in the pit. Oscillatory strontium, barium, and zinc profiles may reflect changing water temperature, diet, or fish metabolism. Lead was detected in very low concentrations and may be related to anthropogenic influence. This closed lake system provides a unique opportunity to study an introduced exotic species in a setting where neither migration nor recruitment have been possible. The fish have successfully occupied the lake and continue to breed despite the influence of the surrounding rocks and local contamination. The chemical record retained within otoliths provides a method of monitoring trace elements affecting fish on a yearly basis and may be regarded as a useful assessment tool for examining the exposure of wild organisms to trace elements.

  16. Use of fuzzy chromatography mass spectrometric (FCMS) fingerprinting and chemometric analysis for differentiation of whole-grain and refined wheat (T. aestivum) flour.

    Science.gov (United States)

    Geng, Ping; Zhang, Mengliang; Harnly, James M; Luthria, Devanand L; Chen, Pei

    2015-10-01

    A fuzzy chromatography mass spectrometric (FCMS) fingerprinting method combined with chemometric analysis has been established for rapid discrimination of whole-grain flour (WF) from refined wheat flour (RF). Bran, germ, endosperm, and WF from three local cultivars or purchased from a grocery store were studied. The state of refinement (whole vs. refined) of wheat flour was differentiated successfully by use of principal-components analysis (PCA) and soft independent modeling of class analogy (SIMCA), despite potential confounding introduced by wheat class (red vs. white; hard vs. soft) or resources (different brands). Twelve discriminatory variables were putatively identified. Among these, dihexoside, trihexoside, apigenin glycosides, and citric acid had the highest peak intensity for germ. Variable line plots indicated phospholipids were more abundant in endosperm. Samples of RF and WF from three cultivars (Hard Red, Hard White, and Soft White) were physically mixed to furnish 20, 40, 60, and 80 % WF of each cultivar. SIMCA was able to discriminate between 100 %, 80 %, 60 %, 40 %, and 20 % WF and 100 % RF. Partial least-squares (PLS) regression was used for prediction of RF-to-WF ratios in the mixed samples. When PLS models were used the relative prediction errors for RF-to-WF ratios were less than 6 %. Graphical Abstract Workflow of targeting discriminatory compounds by use of FCMS and chemometric analysis.

  17. Mass spectrometric monitoring of Sr-enriched bone cements--from in vitro to in vivo.

    Science.gov (United States)

    Rohnke, Marcus; Henss, Anja; Kokesch-Himmelreich, Julia; Schumacher, Matthias; Ray, Seemun; Alt, Volker; Gelinsky, Michael; Janek, Juergen

    2013-11-01

    Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a well-established technique in materials science, but is now increasingly applied also in the life sciences. Here, we demonstrate the potential of this analytical technique for use in the development of new bone implant materials. We tracked strontium-enriched calcium phosphate cements, which were developed for the treatment of osteoporotic bone, from in vitro to in vivo. Essentially, the spatial distribution of strontium in two different types of strontium-modified calcium phosphate cements is analysed by SIMS depth profiling. To gain information about the strontium release kinetics, the cements were immersed for 3, 7, 14 and 21 days in α-MEM and tris(hydroxymethyl)-aminomethane solution and analysed afterwards by ToF-SIMS depth profiling. For cements stored in α-MEM solution an inhibited strontium release was observed. By using principal component analysis to evaluate TOF-SIMS surface spectra, we are able to prove the adsorption of proteins on the cement surface, which inhibit the release kinetics. Cell experiments with human osteoblast-like cells cultured on the strontium-modified cements and subsequent mass spectrometric analysis of the mineralised extracellular matrix (mECM) prove clearly that strontium is incorporated into the mECM of the osteoblast-like cells. Finally, in an animal experiment, the strontium-doped cements are implanted into the femur of osteoporotic rats. After 6 weeks, only a slight release of strontium was found in the vicinity of the implant material. By using ToF-SIMS, it is proven that strontium is localised in regions of newly formed bone but also within the pre-existing tissue.

  18. In situ direct sampling mass spectrometric study on formation of polycyclic aromatic hydrocarbons in toluene pyrolysis.

    Science.gov (United States)

    Shukla, Bikau; Susa, Akio; Miyoshi, Akira; Koshi, Mitsuo

    2007-08-30

    The gas-phase reaction products of toluene pyrolysis with and without acetylene addition produced in a flow tube reactor at pressures of 8.15-15.11 Torr and temperatures of 1136-1507 K with constant residence time (0.56 s) have been detected in an in situ direct sampling mass spectrometric study by using a vacuum ultraviolet single-photon ionization time-of-flight mass spectrometry technique. Those products range from methyl radical to large polycyclic aromatic hydrocarbons (PAHs) of mass 522 amu (C(42)H(18)) including smaller species, radicals, polyynes, and PAHs, together with ethynyl, methyl, and phenyl PAHs. On the basis of observed mass spectra, the chemical kinetic mechanisms of the formation of products are discussed. Especially, acetylene is mixed with toluene to understand the effect of the hydrogen abstraction and acetylene addition (HACA) mechanism on the formation pathways of products in toluene pyrolysis. The most prominent outputs of this work are the direct detection of large PAHs and new reaction pathways for the formation of PAHs with the major role of cyclopenta-fused radicals. The basis of this new reaction route is the appearance of different sequences of mass spectra that well explain the major role of aromatic radicals mainly cyclopenta fused radicals of PAHs resulting from their corresponding methyl PAHs, with active participation of c-C(5)H(5), C(6)H(5), C(6)H(5)CH(2) ,and C(9)H(7) in the formation of large PAHs. The role of the HACA only seemed important for the formation of stable condensed PAHs from unstable primary PAHs with zigzag structure (having triple fusing sites) in one step by ring growth with two carbon atoms.

  19. Rapid Mass Spectrometric Analysis of a Novel Fucoidan, Extracted from the Brown Alga Coccophora langsdorfii

    Directory of Open Access Journals (Sweden)

    Stanislav D. Anastyuk

    2014-01-01

    Full Text Available The novel highly sulfated (35% fucoidan fraction Cf2 , which contained, along with fucose, galactose and traces of xylose and uronic acids was purified from the brown alga Coccophora langsdorfii. Its structural features were predominantly determined (in comparison with fragments of known structure by a rapid mass spectrometric investigation of the low-molecular-weight fragments, obtained by “mild” (5 mg/mL and “exhaustive” (maximal concentration autohydrolysis. Tandem matrix-assisted laser desorption/ionization mass spectra (MALDI-TOF/TOFMS of fucooligosaccharides with even degree of polymerization (DP, obtained by “mild” autohydrolysis, were the same as that observed for fucoidan from Fucus evanescens, which have a backbone of alternating (1 → 3- and (1 → 4 linked sulfated at C-2 and sometimes at C-4 of 3-linked α-L-Fucp residues. Fragmentation patterns of oligosaccharides with odd DP indicated sulfation at C-2 and at C-4 of (1 → 3 linked α-L-Fucp residues on the reducing terminus. Minor sulfation at C-3 was also suggested. The “exhaustive” autohydrolysis allowed us to observe the “mixed” oligosaccharides, built up of fucose/xylose and fucose/galactose. Xylose residues were found to occupy both the reducing and nonreducing termini of FucXyl disaccharides. Nonreducing galactose residues as part of GalFuc disaccharides were found to be linked, possibly, by 2-type of linkage to fucose residues and were found to be sulfated, most likely, at position C-2.

  20. Single-walled carbon nanotubes coated fibers for solid-phase microextraction and gas chromatography-mass spectrometric determination of pesticides in Tea samples.

    Science.gov (United States)

    Wu, Fang; Lu, Wanping; Chen, Jinghua; Liu, Wei; Zhang, Lan

    2010-08-15

    Using a single-walled carbon nanotubes (SWCNTs) as stationary phase of solid-phase microextraction (SPME) fibers, a simple, low cost and environmentally friendly method for extraction of 13 pesticides in Tea samples has been developed following gas chromatography-mass spectrometric determination. Potential factors affecting the extraction efficiency were investigated and optimized, including extraction and desorption time, extraction temperature, stirring rate, solution pH and ionic strength. Under optimized conditions, the linearity of the developed method was in the range of 0.125-25 ng/mL with correlation coefficients greater than 0.9928 and the limits of detections (LODs) were 0.027-0.23 ng/mL (S/N=3). Meanwhile, the relative standard deviations (RSDs) for five successive measurements with single fiber, fiber-to-fiber, day-to-day were 2.3-13.0, 8.2-14.6 and 4.1-12.5%, respectively, indicating good reproducibility of the proposed method. The fiber had high extraction efficiency for studied pesticides in comparison with commercial poly(dimethylsiloxane) (PDMS) and polyacrylate (PA) fibers and could be used for more than 70 times without decrease of efficiency. The developed method was successfully applied for the analysis of real samples including green Tea, oolong Tea, white Tea, and flower Tea, and the recoveries of the pesticides spiked in these samples ranged from 75.1 to 118.4%. Chlorfenapyr and lambda-cyhalothrin were found in the Tea samples bought randomly from local market. The results demonstrated that the developed SWCNTs-SPME method was a simple, efficient pretreatment and enrichment procedure for pesticides in complex matrices.

  1. Mass spectrometric fragmentation pathways of isotope labeled 2,5-disubstituted-1,3,4-oxadiazoles and thiadiazoles

    Science.gov (United States)

    Franski, Rafal; Gierczyk, Blazej; Schroeder, Grzegorz

    2004-01-01

    The mass spectrometric decomposition of protonated, lithiated and methylated (quaternary derivatives) 2-(4'-methoxy)phenyl-5-phenyl-1,3,4-oxadiazoles, containing 13C atom at 5 position of oxadiazole ring as well as its thia correspondent is discussed. The electron-donor properties of C-4' substituent favor cationization of N(3) atom and as a consequence, the losses of HNC(2)O, LiNC(2)O, CH3NC(2)O molecules are favored over HNC(5)O, LiNC(5)O, CH3NC(5)O molecules. Analogous results have been obtained for HNCS and CH3NCS elimination from thiadiazole.

  2. Gamma-ray spectrometric dating of late Homo erectus skulls from Ngandong and Sambungmacan, Central Java, Indonesia.

    Science.gov (United States)

    Yokoyama, Yuji; Falguères, Christophe; Sémah, François; Jacob, Teuku; Grün, Rainer

    2008-08-01

    Hominid fossils from Ngandong and Sambungmacan, Central Java, Indonesia, are considered to be the most anatomically derived and youngest representatives of Homo erectus. Nondestructive gamma-ray spectrometric dating of three of these Homo erectus skulls showed that all samples underwent uranium leaching. Nevertheless, we could establish minimum age estimates of around 40ka, with an upper age limit of around 60 to 70ka. This means that the Homo erectus of Java very likely survived the Toba eruption and may have been contemporaneous with the earliest Homo sapiens in Southeast Asia and Australasia.

  3. The high-performance liquid chromatography/multistage electrospray mass spectrometric investigation and extraction optimization of beech (Fagus sylvatica L.) bark polyphenols.

    Science.gov (United States)

    Hofmann, Tamás; Nebehaj, Esztella; Albert, Levente

    2015-05-08

    The aim of the present work was the high-performance liquid chromatographic separation and multistage mass spectrometric characterization of the polyphenolic compounds of beech bark, as well as the extraction optimization of the identified compounds. Beech is a common and widely used material in the wood industry, yet its bark is regarded as a by-product. Using appropriate extraction methods these compounds could be extracted and utilized in the future. Different extraction methods (stirring, sonication, microwave assisted extraction) using different solvents (water, methanol:water 80:20 v/v, ethanol:water 80:20 v/v) and time/temperature schedules have been compared basing on total phenol contents (Folin-Ciocâlteu) and MRM peak areas of the identified compounds to investigate optimum extraction efficiency. Altogether 37 compounds, including (+)-catechin, (-)-epicatechin, quercetin-O-hexoside, taxifolin-O-hexosides (3), taxifolin-O-pentosides (4), B-type (6) and C-type (6) procyanidins, syringic acid- and coumaric acid-di-O-glycosides, coniferyl alcohol- and sinapyl alcohol-glycosides, as well as other unknown compounds with defined [M-H](-) m/z values and MS/MS spectra have been tentatively identified. The choice of the method, solvent system and time/temperature parameters favors the extraction of different types of compounds. Pure water can extract compounds as efficiently as mixtures containing organic solvents under high-pressure and high temperature conditions. This supports the implementation of green extraction methods in the future. Extraction times that are too long and high temperatures can result in the decrease of the concentrations. Future investigations will focus on the evaluation of the antioxidant capacity and utilization possibilities of the prepared extracts.

  4. In situ probing of cholesterol in astrocytes at the single-cell level using laser desorption ionization mass spectrometric imaging with colloidal silver.

    Science.gov (United States)

    Perdian, D C; Cha, Sangwon; Oh, Jisun; Sakaguchi, Donald S; Yeung, Edward S; Lee, Young Jin

    2010-04-30

    Mass spectrometric imaging has been utilized to localize individual astrocytes and to obtain cholesterol populations at the single-cell level in laser desorption ionization (LDI) with colloidal silver. The silver ion adduct of membrane-bound cholesterol was monitored to detect individual cells. Good correlation between mass spectrometric and optical images at different cell densities indicates the ability to perform single-cell studies of cholesterol abundance. The feasibility of quantification is confirmed by the agreement between the LDI-MS ion signals and the results from a traditional enzymatic fluorometric assay. We propose that this approach could be an effective tool to study chemical populations at the cellular level.

  5. Method-MS. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Skipperud, L.; Popic, J.M. (Norwegian Univ. of Life Science (UMB), Isotope Lab. (Norway)); Roos, P. (Technical Univ. of Denmark, Risoe National Lab. for Sustainable Energy, Roskilde (Denmark)); Salminen, S. (Univ. of Helsinki (UH) (Finland)); Nygren, U. (Swedish Defence Research Agency (FOI) (Sweden)); Sigmarsson, O.; Palsson, S.E. (Univ. of Iceland/Icelandic Radiation Protection Institute (Iceland))

    2011-05-15

    Radiometric determination methods, such as alpha spectrometry require long counting times when low activities are to be determined. Mass spectrometric techniques as Inductively Coupled Plasma Mass Spectrometry (ICP-MS), Thermal Ionisation Mass Spectrometry (TIMS) and Accelerator Mass Spectrometry (AMS) have shown several advantages compared to traditional methods when measuring long-lived radionuclides. Mass spectrometric methods for determination of very low concentrations of elemental isotopes, and thereby isotopic ratios, have been developed using a variety of ion sources. Although primarily applied to the determination of the lighter stable element isotopes and radioactive isotopes in geological studies, the techniques can equally well be applied to the measurement of activity concentrations of long-lived low-level radionuclides in various samples using 'isotope dilution' methods such as those applied in inductively coupled plasma mass spectrometry (ICP-MS). Due to the low specific activity of long-lived radionuclides, many of these are more conveniently detected using mass spectrometric techniques. Mass spectrometry also enables the individual determination of Pu-239 and Pu-240, which cannot be obtained by alpha spectrometry. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) are rapidly growing techniques for the ultra-trace analytical determination of stable and long-lived isotopes and have a wide potential within environmental science, including ecosystem tracers and radio ecological studies. Such instrumentation, of course needs good radiochemical separation, to give best performance. The objectives of the project is to identify current needs and problems within low-level determination of long-lived radioisotopes by ICP-MS, to perform intercalibration and development and improvement of ICP-MS methods for the measurement of radionuclides and isotope ratios and to develop new methods based on modified separation chemistry applied to new

  6. method

    Directory of Open Access Journals (Sweden)

    L. M. Kimball

    2002-01-01

    Full Text Available This paper presents an interior point algorithm to solve the multiperiod hydrothermal economic dispatch (HTED. The multiperiod HTED is a large scale nonlinear programming problem. Various optimization methods have been applied to the multiperiod HTED, but most neglect important network characteristics or require decomposition into thermal and hydro subproblems. The algorithm described here exploits the special bordered block diagonal structure and sparsity of the Newton system for the first order necessary conditions to result in a fast efficient algorithm that can account for all network aspects. Applying this new algorithm challenges a conventional method for the use of available hydro resources known as the peak shaving heuristic.

  7. Mass Spectrometric Investigation of Silicon Extremely Enriched in (28)Si: From (28)SiF4 (Gas Phase IRMS) to (28)Si Crystals (MC-ICP-MS).

    Science.gov (United States)

    Pramann, Axel; Rienitz, Olaf

    2016-06-01

    A new generation of silicon crystals even further enriched in (28)Si (x((28)Si) > 0.999 98 mol/mol), recently produced by companies and institutes in Russia within the framework of a project initiated by PTB, were investigated with respect to their isotopic composition and molar mass M(Si). A modified isotope dilution mass spectrometric (IDMS) method treating the silicon as the matrix containing a so-called virtual element (VE) existing of the isotopes (29)Si and (30)Si solely and high resolution multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) were applied in combination. This method succeeds also when examining the new materials holding merely trace amounts of (29)Si (x((29)Si) ≈ 5 × 10(-6) mol/mol) and (30)Si (x((30)Si) ≈ 7 × 10(-7) mol/mol) extremely difficult to detect with lowest uncertainty. However, there is a need for validating the enrichment in (28)Si already in the precursor material of the final crystals, silicon tetrafluoride (SiF4) gas prior to crystal production. For that purpose, the isotopic composition of selected SiF4 samples was determined using a multicollector magnetic sector field gas-phase isotope ratio mass spectrometer. Contaminations of SiF4 by natural silicon due to storing and during the isotope ratio mass spectrometry (IRMS) measurements were observed and quantified. The respective MC-ICP-MS measurements of the corresponding crystal samples show-in contrast-several advantages compared to gas phase IRMS. M(Si) of the new crystals were determined to some extent with uncertainties urel(M) Si)) on the degree of enrichment in (28)Si. This leads to a reduction of urel(M(Si)) during the past decade by almost 3 orders of magnitude and thus further reduces the uncertainty of the Avogadro constant NA which is one of the preconditions for the redefinition of the SI unit kilogram.

  8. High Throughput In Situ DDA Analysis of Neuropeptides by Coupling Novel Multiplex Mass Spectrometric Imaging (MSI) with Gas-Phase Fractionation

    Science.gov (United States)

    OuYang, Chuanzi; Chen, Bingming; Li, Lingjun

    2015-12-01

    Matrix-assisted laser desorption/ionization (MALDI) mass spectrometric imaging (MSI) is a powerful tool to map the spatial distribution of biomolecules on tissue sections. Recent developments of hybrid MS instruments allow combination of different types of data acquisition by various mass analyzers into a single MSI analysis, which reduces experimental time and sample consumptions. Here, using the well-characterized crustacean nervous system as a test-bed, we explore the utility of high resolution and accurate mass (HRAM) MALDI Orbitrap platform for enhanced in situ characterization of the neuropeptidome with improved chemical information. Specifically, we report on a multiplex-MSI method, which combines HRAM MSI with data dependent acquisition (DDA) tandem MS analysis in a single experiment. This method enables simultaneous mapping of neuropeptide distribution, sequence validation, and novel neuropeptide discovery in crustacean neuronal tissues. To enhance the dynamic range and efficiency of in situ DDA, we introduced a novel approach of fractionating full m/z range into several sub-mass ranges and embedding the setup using the multiplex-DDA-MSI scan events to generate pseudo fractionation before MS/MS scans. The division of entire m/z into multiple segments of m/z sub-ranges for MS interrogation greatly decreased the complexity of molecular species from tissue samples and the heterogeneity of the distribution and variation of intensities of m/z peaks. By carefully optimizing the experimental conditions such as the dynamic exclusion, the multiplex-DDA-MSI approach demonstrates better performance with broader precursor coverage, less biased MS/MS scans towards high abundance molecules, and improved quality of tandem mass spectra for low intensity molecular species.

  9. Characterization of therapeutic antibodies and related products by two-dimensional liquid chromatography coupled with UV absorbance and mass spectrometric detection.

    Science.gov (United States)

    Stoll, Dwight; Danforth, John; Zhang, Kelly; Beck, Alain

    2016-10-01

    The development of analytical tools for the characterization of large biomolecules is an emerging and rapidly evolving area. This development activity is motivated largely by the current trend involving the increase in development and use of large biomolecules for therapeutic uses. Given the inherent complexity of these biomolecules, which arises from their sheer size and possibilities for chemical modification as well as changes over time (e.g., through modification in solution, aggregation), two-dimensional liquid chromatography (2D-LC) has attracted considerable interest as an analytical tool to address the challenges faced in characterizing these materials. The immediate potential benefits of 2D-LC over conventional one-dimensional liquid chromatography in this context include: (1) higher overall resolving power; (2) complementary information gained from two dimensions of separation in a single analysis; and (3) enabling indirect coupling of separation modes that are inherently incompatible with mass spectrometric (MS) detection (e.g., ion-exchange, because of high-salt eluents) to MS through a more compatible second dimension separation such as reversed-phase LC. In this review we summarize the work in this area, most of which has occurred in the past five years. Although the future is bright for further development in this area, some challenges have already been addressed through new 2D-LC methods. These include: (1) deep characterization of monoclonal antibodies to understand charge heterogeneity, glycosylation patterns, and other modifications; (2) characterization of antibody-drug conjugates to understand the extent and localization of small molecule conjugation; (3) detailed study of excipients in protein drug formulations; and (4) detection of host-cell proteins on biotherapeutic molecule preparations. We fully expect that in the near future we will see this list expanded, and that continued development will lead to methods with further improved

  10. Liquid chromatography-tandem mass spectrometric assay for the tyrosine kinase inhibitor afatinib in mouse plasma using salting-out liquid-liquid extraction

    NARCIS (Netherlands)

    Sparidans, Rolf W; van Hoppe, Stephanie; Rood, Johannes J M; Schinkel, Alfred H; Schellens, Jan H M; Beijnen, Jos H

    2016-01-01

    A quantitative bioanalytical liquid chromatography-tandem mass spectrometric (LC-MS/MS) assay for afatinib, an irreversible inhibitor of the ErbB (erythroblastic leukemia viral oncogene homolog) tyrosine kinase family, was developed and validated. Plasma samples were pre-treated using salting-out as

  11. Ultrafast and high-throughput mass spectrometric assay for therapeutic drug monitoring of antiretroviral drugs in pediatric HIV-1 infection applying dried blood spots.

    NARCIS (Netherlands)

    Meesters, R.J.; Kampen, J.J. van; Reedijk, M.L.; Scheuer, R.D.; Dekker, L.J.; Burger, D.M.; Hartwig, N.G.; Osterhaus, A.D.; Luider, T.M.; Gruters, R.A.

    2010-01-01

    Kaletra (Abott Laboratories) is a co-formulated medication used in the treatment of HIV-1-infected children, and it contains the two antiretroviral protease inhibitor drugs lopinavir and ritonavir. We validated two new ultrafast and high-throughput mass spectrometric assays to be used for therapeuti

  12. Electronic structure and bonding in the RhC molecule by all-electron ab initio HF–Cl calculations and mass spectrometric measurements

    DEFF Research Database (Denmark)

    Shim, Irene; Gingerich, K. A.

    1984-01-01

    in a singly occupied, nonbonding orbital. The chemical bond in RhC is polar with a charge transfer from Rh to C giving rise to a dipole moment of 2.82 D at the experimental equilibrium distance. Mass spectrometric equilibrium measurements over the temperature range 1970–2806 K have resulted in the selected...

  13. Electronic states and nature of bonding in the molecule YC by all electron ab initio multiconfiguration self-consistent-field calculations and mass spectrometric equilibrium experiments

    DEFF Research Database (Denmark)

    Shim, Irene; Pelino, Mario; Gingerich, Karl A.

    1992-01-01

    , and they hardly contribute to the bonding. The chemical bond in the YC molecule is polar with charge transfer from Y to C giving rise to a dipole moment of 3.90 D at 3.9 a.u. in the 4PI ground state. Mass spectrometric equilibrium investigations in the temperature range 2365-2792 K have resulted...

  14. 2DB: a Proteomics database for storage, analysis, presentation, and retrieval of information from mass spectrometric experiments

    Directory of Open Access Journals (Sweden)

    Hippler Michael

    2008-07-01

    Full Text Available Abstract Background The amount of information stemming from proteomics experiments involving (multi dimensional separation techniques, mass spectrometric analysis, and computational analysis is ever-increasing. Data from such an experimental workflow needs to be captured, related and analyzed. Biological experiments within this scope produce heterogenic data ranging from pictures of one or two-dimensional protein maps and spectra recorded by tandem mass spectrometry to text-based identifications made by algorithms which analyze these spectra. Additionally, peptide and corresponding protein information needs to be displayed. Results In order to handle the large amount of data from computational processing of mass spectrometric experiments, automatic import scripts are available and the necessity for manual input to the database has been minimized. Information is in a generic format which abstracts from specific software tools typically used in such an experimental workflow. The software is therefore capable of storing and cross analysing results from many algorithms. A novel feature and a focus of this database is to facilitate protein identification by using peptides identified from mass spectrometry and link this information directly to respective protein maps. Additionally, our application employs spectral counting for quantitative presentation of the data. All information can be linked to hot spots on images to place the results into an experimental context. A summary of identified proteins, containing all relevant information per hot spot, is automatically generated, usually upon either a change in the underlying protein models or due to newly imported identifications. The supporting information for this report can be accessed in multiple ways using the user interface provided by the application. Conclusion We present a proteomics database which aims to greatly reduce evaluation time of results from mass spectrometric experiments and enhance

  15. Peptides from two sanguinovorous leeches analyzed by ultra-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight mass spectrometric detector

    Directory of Open Access Journals (Sweden)

    Ling Xiao

    2015-01-01

    Full Text Available Background: Hirudo nipponica Whitman and Poecilobdella manillensis Lesson fall into the family of Hirudinidae Whitman, both of them are sanguinovorous leeches and used a anticoagulant medicines in China. Their medicinal parts are the dried bodies. However, the peptides in the dried body of the two leeches have not been very clear up to now. Objective: To analyze the peptides from two sanguinovorous leeches, H. nipponica and P. manillensis. Materials and Methods: In this article it is reported that the peptides were obtained from anticoagulant active extracted parts of dried bodies of the two leeches and their molecular weights were analyzed by ultra-performance liquid chromatography with electrospray ionization quadrupole time-of-flight mass spectrometry mass spectrometric detector online. Results: Three peptide components were identified from H. nipponica with their molecular weight separately 14998, 15988, and 15956, six peptide components were identified from P. manillensis with molecular weight 9590, 13642, 14998, 17631, 15988, and 16567. Two of peptides from P. manillensis have the same molecular weight 14998 and 15988 as that in H. nipponica. Conclusion: And the two peptides are the main peaks in the base peak ion chromatogram because they occupied a large ratio of total base peak area. Hence the composition of the extracted active part of the two leeches are very close, difference is in that the extract of P. manillensis has more small peptide peaks, but the extract of H. nipponica has not. Furthermore, the tryptic digestion hydrolysates of the extracted active part of each sample were analyzed and the results showed that there were four peaks which only exist in P. manillensis, but not in Hirudo nipponia. They may be the identified peak between the two leeches. This work support the viewpoint that P. manillensis can be used as a medicinal leech as H. nipponia and these peptide components of dried bodies of the two species leeches are a

  16. Liquid chromatography tandem mass spectrometric quantitation of sulfamethazine and its metabolites: direct analysis of swine urine by triple quadrupole and by ion trap mass spectrometry.

    Science.gov (United States)

    Bartolucci, G; Pieraccini, G; Villanelli, F; Moneti, G; Triolo, A

    2000-01-01

    This work describes a new method for the quantitation of trace amounts of sulfamethazine (SMZ) and its main metabolite, N4-acetylsulfamethazine (Ac-SMZ), in swine urine, using high-performance liquid chromatography (HPLC) tandem mass spectrometric analysis of crude urine after addition of internal standard and simple dilution with water. The aim was to determine whether residues of this sulfamidic drug, normally administered to swine in order to prevent infectious diseases, were present in urine at levels lower than those permitted by regulatory authorities before human consumption (EU Project SMT, contract number CT 96-2092). A 10 microL volume of diluted urine was injected into a very short, narrow-bore chromatographic column (Zorbax SB-C18 2.1 i. d. x30 mm length, 3.5 microm pore size). Elution of the analytes of interest was achieved in less than seven minutes using a rapid gradient (from 20 to 80% methanol in 3 minutes). Either a PE Sciex API 365 triple quadrupole (QqQ), operated in the selected reaction monitoring (SRM) mode, or a Finnigan LCQ ion trap (IT) mass spectrometer, operated in narrow-range product ion scan, was used as the final detector. Electrospray (ESI) was used as the ionization technique. A comparison of the two tandem mass spectrometers was performed by analyzing the same set of test samples, at three concentration levels, on three different days. Linearity of responses of the calibration standards, intra- and inter-assay precision of the samples, specificity and limits of detection were evaluated for both systems. Both the QqQ and the IT instrument was suitable for rapid, sensitive and specific determination of the analytes, although the overall performance of the QqQ was slightly superior in terms of linearity, precision and sensitivity.

  17. Degradation of Adenine on the Martian Surface in the Presence of Perchlorates and Ionizing Radiation: A Reflectron Time-of-flight Mass Spectrometric Study

    Science.gov (United States)

    Góbi, Sándor; Bergantini, Alexandre; Kaiser, Ralf I.

    2017-04-01

    The aim of the present work is to unravel the radiolytic decomposition of adenine (C5H5N5) under conditions relevant to the Martian surface. Being the fundamental building block of (deoxy)ribonucleic acids, the possibility of survival of this biomolecule on the Martian surface is of primary importance to the astrobiology community. Here, neat adenine and adenine–magnesium perchlorate mixtures were prepared and irradiated with energetic electrons that simulate the secondary electrons originating from the interaction of the galactic cosmic rays with the Martian surface. Perchlorates were added to the samples since they are abundant—and therefore relevant oxidizers on the surface of Mars—and they have been previously shown to facilitate the radiolysis of organics such as glycine. The degradation of the samples were monitored in situ via Fourier transformation infrared spectroscopy and the electron ionization quadruple mass spectrometric method; temperature-programmed desorption profiles were then collected by means of the state-of-the-art single photon photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS), allowing for the detection of the species subliming from the sample. The results showed that perchlorates do increase the destruction rate of adenine by opening alternative reaction channels, including the concurrent radiolysis/oxidation of the sample. This new pathway provides a plethora of different radiolysis products that were identified for the first time. These are carbon dioxide (CO2), isocyanic acid (HNCO), isocyanate (OCN‑), carbon monoxide (CO), and nitrogen monoxide (NO); an oxidation product containing carbonyl groups (R1R2–C=O) with a constrained five-membered cyclic structure could also be observed. Cyanamide (H2N–C≡N) was detected in both irradiated samples as well.

  18. Application of a Liquid Extraction Based Sealing Surface Sampling Probe for Mass Spectrometric Analysis of Dried Blood Spots and Mouse Whole-Body Thin Tissue Sections

    Energy Technology Data Exchange (ETDEWEB)

    Van Berkel, Gary J [ORNL; Kertesz, Vilmos [ORNL

    2009-01-01

    The utility of a liquid extraction based sealing surface sampling probe (SSSP) for the direct mass spectrometric analysis of targeted drugs and metabolites in dried blood spots (DBSs) and whole mouse thin tissue sections was demonstrated. The accuracy and precision for the quantitative analysis of a minimum of 50 ng/mL sitamaquine or acetaminophen in DBSs on paper were well within the required 15% dictated by internationally recognized acceptance criteria for assay validations. Analysis of whole-body mouse thin tissue sections from animals dosed with propranolol, adhered to an adhesive tape substrate, provided semi-quantitative information for propranolol and its hydroxyproranolol glucuronide metabolite within specific organs of the tissue. The relative abundances recorded for the two compounds in the brain, lung, kidney and liver were in nominal agreement with previously reported amounts based on analysis using a liquid microjunction surface sampling probe (LMJ-SSP), and whole-body autoradiography (WBA) and HPLC-MS analysis. The ability to sample and analyze from tape-adhered tissue samples, which are generally employed in WBA analysis, presents the possibility of consecutive WBA and SSSP-MS analysis of the same tissue section. This would facilitate assignment, and possibly quantitation, of the different molecular forms of total drug related material detected in the WBA analysis. The flexibility to sample larger or smaller spot sizes, alternative probe sealing mechanisms, and a reduction in internal volumes and associated sample carryover issues will be among the first simple improvements necessary to make the SSSP-MS method a practical DBS and/or thin tissue section analysis tool or to expand its use to other surface sampling applications.

  19. Method

    Directory of Open Access Journals (Sweden)

    Xixin Wang

    2012-01-01

    Full Text Available ZrO2 nanotube arrays were prepared by anodization method in aqueous electrolyte containing (NH42SO4 and NH4F. The morphology and structure of nanotube arrays were characterized through scanning electron microscope, X-ray diffraction, and infrared spectra analysis. The zirconia nanotube arrays were used as catalyst in esterification reaction. The effects of calcination temperature and electrolyte concentration on catalytic esterification activity have been investigated in detail. Experiments indicate that nanotube arrays have highest catalytic activity when the concentration of (NH42SO4 is 1 mol/L, the concentration of NH4F is 1 wt%, and the calcination temperature is 400°C. Esterification reaction yield of as much as 97% could be obtained under optimal conditions.

  20. Combined mass spectrometric and chromatographic methods for in-depth analysis of phenolic secondary metabolites in barley leaves.

    Science.gov (United States)

    Piasecka, Anna; Sawikowska, Aneta; Krajewski, Paweł; Kachlicki, Piotr

    2015-03-01

    Structural analysis via HPLC-ESI-MSn, UPLC-HESI-MS/MS and NMR reported 152 phenolic secondary metabolites in spring barley seedlings (Hordeum vulgare L.). Flavonoids with various patterns of glycosylation and acylation, as well as hydroxycinnamic acid glycosides, esters and amides, were identified in methanolic extracts from leaves of nine varieties of barley originating from different regions of the world. Hordatines derivatives, flavones acylated directly on the aglycone, and hydroxyferulic acid derivatives deserve special attention. Preparative chromatography enabled characterization of a number of compounds at trace levels with the 6-C-[6″-O-glycosyl]-glycosides and the 6-C-[2″,6″-di-O-glycosides]-glucoside structure of flavones. Derivatives of flavonols, quercetin and isorhamnetin were observed only in Syrian varieties. The ultra performance liquid chromatography profiles of UV-absorbing secondary metabolites were used for chemotaxonomic comparison between nine varieties of barley from different climatic conditions. The hierarchical clustering of bred lines from the Fertile Crescent and European and American varieties indicates a great diversity of chemical phenotypes within barley species.

  1. 40 CFR Appendix C to Part 136 - Inductively Coupled Plasma-Atomic Emission Spectrometric Method for Trace Element Analysis of...

    Science.gov (United States)

    2010-07-01

    ... 2 are intended for use only as a rudimentary guide for the indication of potential spectral... and repeat the calibration. 13.Precision and Accuracy 13.1An interlaboratory study of metal analyses... in Academic Chemistry Laboratories, American Chemical Society Publication, Committee on...

  2. Extraction chromatographic methods in the sample preparation sequence for thermal ionization mass spectrometric analysis of plutonium isotopes.

    Science.gov (United States)

    Grate, Jay W; O'Hara, Matthew J; Farawila, Anne F; Douglas, Matthew; Haney, Morgan M; Petersen, Steven L; Maiti, Tapas C; Aardahl, Christopher L

    2011-12-01

    A sample preparation sequence for actinide isotopic analysis by thermal ionization mass spectrometry (TIMS) is described that includes column-based extraction chromatography as the first separation step, followed by anion-exchange column separations. The sequence is designed to include a wet ashing step after the extraction chromatography to prevent any leached extractant or oxalic acid eluent reagents from interfering with subsequent separations, source preparation, or TIMS ionization. TEVA resin and DGA resin materials, containing extractants that consist only of C, N, O, and H atoms, were investigated for isolation of plutonium. Radiotracer level studies confirmed expected high yields from column-based separation procedures. Femtogram-level studies were carried out with TIMS detection, using multiple monoisotopic spikes applied sequentially throughout the separation sequence. Pu recoveries were 87% and 86% for TEVA and DGA resin separations, respectively. The Pu recoveries from 400 μL anion-exchange column separation sequences were 89% and 93% for trial sequences incorporating TEVA and DGA resin. Thus, a prior extraction chromatography step in the sequence did not interfere with the subsequent anion-exchange separation when a simple wet ash step was carried out in between these column separations. The average measurement efficiency for Pu, encompassing the chemical separation recoveries and the TIMS ionization efficiency, was 2.73% ± 0.77% (2σ) for the DGA resin trials and 2.67% ± 0.54% for the TEVA resin trials, compared to 3.41% and 2.37% (average 2.89%) for two control trials. These compare with an average measurement efficiency of 2.78% ± 1.70%, n = 33 from process benchmark analyses using Pu spikes processed through a sequence of oxalate precipitation, wet ash, iron hydroxide precipitation, and anion-exchange column separations. We conclude that extraction chromatography can be a viable separation procedure as part of a multistep sequence for TIMS sample preparation.

  3. Characterization of human myotubes from type 2 diabetic and non-diabetic subjects using complementary quantitative mass spectrometric methods

    DEFF Research Database (Denmark)

    Thingholm, Tine E; Bak, Steffen; Beck-Nielsen, Henning

    2011-01-01

    2 diabetes. Several abnormalities have been identified in skeletal muscle from type 2 diabetic subjects, however, the exact molecular mechanisms leading to the diabetic phenotype has still not been found. Here we present a large-scale study in which we combine a quantitative proteomic discovery....... Twelve proteins were, however, differentially expressed between the three different groups. Thirty-six proteins were chosen for further analysis and validation using SRM based on the regulation identified in the iTRAQ discovery study. The abundance of adenosine deaminase was considerably down...

  4. Simultaneous quantification of anidulafungin and caspofungin in plasma by an accurate and simple liquid chromatography tandem mass-spectrometric method

    NARCIS (Netherlands)

    Wanrooy, M.J. van; Santoe, R.N.; Elst, K.C. van der; Wilmer, C.M.; Hateren, K. van; Wessels, A.M.; Greijdanus, B.; Alffenaar, J.W.C.; Uges, D.R.A.

    2013-01-01

    INTRODUCTION: Echinocandins are a valuable addition for the treatment of invasive fungal infections, as they are efficacious, demonstrate low toxicity, and have limited drug-drug interactions. In specific clinical situations when altered pharmacokinetics can be expected or dosing guidelines are conf

  5. Selection and optimization of spectrometric amplifiers for gamma spectrometry: part II - linearity, live time correction factors and software; Seleccion y optimizacion de amplificadores espectrometricos para espectrometria gamma: parte II - linealidad, tiempo vivo, software

    Energy Technology Data Exchange (ETDEWEB)

    Moraes, Marco Antonio Proenca Vieira de; Pugliesi, Reinaldo [Instituto de Pesquisas Energeticas e Nucleares (IPEN), Sao Paulo, SP (Brazil)

    1996-07-01

    The objective of the present work was to establish simple criteria to choose the best combination of electronic modules to achieve an adequate high resolution gamma spectrometer. Linearity, live time correction factors and softwares of a gamma spectrometric system composed by a Hp Ge detector have been studied by using several kinds of spectrometric amplifiers: Canberra 2021, Canberra 2025, Ortec 673 and Tennelec 244 and the MCA cards Ortec and Nucleus. The results showed low values of integral non-linearity for all spectrometric amplifiers connected to the Ortec and Nucleus boards. The MCA card should be able to correct amplifier dead time for 17 kcps count rates. (author)

  6. Evaluation of radioactive environmental hazards in Area-3, Northern Palmyrides, Central Syria using airborne spectrometric gamma technique.

    Science.gov (United States)

    Asfahani, J; Aissa, M; Al-Hent, R

    2016-01-01

    Airborne spectrometric gamma data are used in this paper to estimate the degree of radioactive hazard on humanity in Area-3, Northern Palmyrides, Central Syria. Exposure Rate (ER), Absorbed Dose Rate (ADR), Annual Effective Dose Rate (AEDR), and Heat Production (HP) of the eleven radiometric units included in the established lithological scored map in the study area have been computed to evaluate the radiation background influence in humans. The results obtained indicate that a human body in Area-3 is subjected to radiation hazards in the acceptable limits for long duration exposure. The highest radiogenetic heat production values in Area-3 correspond to the phosphatic locations characterized by relatively high values of uranium and thorium.

  7. Ultraviolet irradiation-induced substitution of fluorine with hydroxyl radical for mass spectrometric analysis of perfluorooctane sulfonyl fluoride.

    Science.gov (United States)

    Wang, Peng; Tang, Xuemei; Huang, Lulu; Kang, Jie; Zhong, Hongying

    2016-01-28

    A rapid and solvent free substitution reaction of a fluorine atom in perfluorooctane sulfonyl fluoride (PFOSF) with a hydroxyl radical is reported. Under irradiation of ultraviolet laser on semiconductor nanoparticles or metal surfaces, hydroxyl radicals can be generated through hole oxidization. Among all fluorine atoms of PFOSF, highly active hydroxyl radicals specifically substitute the fluorine of sulfonyl fluoride functional group. Resultant perfluorooctane sulfonic acid is further ionized through capture of photo-generated electrons that switch the neutral molecules to negatively charged odd electron hypervalent ions. The unpaired electron subsequently initiates α O-H bond cleavage and produces perfluorooctane sulfonate negative ions. Hydroxyl radical substitution and molecular dissociation of PFOSF have been confirmed by masses with high accuracy and resolution. It has been applied to direct mass spectrometric imaging of PFOSF adsorbed on surfaces of plant leaves.

  8. Mass spectrometric study of the thermochemistry of gaseous EuTiO3 and TiO2

    Science.gov (United States)

    Balducci, G.; Gigli, G.; Guido, M.

    1985-08-01

    The gaseous molecule EuTiO3 has been investigated in a high temperature mass spectrometric study of vapors over the europium-titanium-oxygen system. From the enthalpy of reaction: EuTiO3(g)=EuO(g)+TiO2(g) and proper ancillary data, the atomization energy of this molecule has been determined. In addition, from the study of the gaseous exchange reaction: TiO2(g)+Eu(g)=TiO(g)+EuO(g) the dissociation energy of TiO2(g) has been derived and compared with previous results. The dissociation energies proposed are: D○0,at(EuTiO3) =2278±28 kJ mol-1 and D○0,at(TiO2) =1260±12 kJ mol-1.

  9. Method

    Directory of Open Access Journals (Sweden)

    Andrey Gnatov

    2015-01-01

    Full Text Available Recently repair and recovery vehicle body operations become more and more popular. A special place here is taken by equipment that provides performance of given repair operations. The most interesting things are methods for recovery of car body panels that allow the straightening without disassembling of car body panels and damaging of existing protective coating. Now, there are several technologies for repair and recovery of car body panels without their disassembly and dismantling. The most perspective is magnetic-pulse technology of external noncontact straightening. Basics of magnetic-pulse attraction, both ferromagnetic and nonferromagnetic thin-walled sheet metal, are explored. Inductor system calculation models of magnetic-pulse straightening tools are presented. Final analytical expressions for excited efforts calculation in the tools under consideration are introduced. According to the obtained analytical expressions, numerical evaluations of excited forces were executed. The volumetric epures of the attractive force radial distributions for different types of inductors were built. The practical testing of magnetic-pulse straightening with research tools is given. Using the results of the calculations we can create effective tools for an external magnetic-pulse straightening of car body panels.

  10. Vitamin B6: deficiency diseases and methods of analysis.

    Science.gov (United States)

    Ahmad, Iqbal; Mirza, Tania; Qadeer, Kiran; Nazim, Urooj; Vaid, Faiyaz Hm

    2013-09-01

    Vitamin B6 (pyridoxine) is closely associated with the functions of the nervous, immune and endocrine systems. It also participates in the metabolic processes of proteins, lipids and carbohydrates. Pyridoxine deficiency may result in neurological disorders including convulsions and epileptic encephalopathy and may lead to infant abnormalities. The Intravenous administration of pyridoxine to patients results in a dramatic cessation of seizures. A number of analytical methods were developed for the determination of pyridoxine in different dosage forms, food materials and biological fluids. These include UV spectrometric, spectrofluorimetric, mass spectrometric, thin-layer and high-performance liquid chromatographic, electrophoretic, electrochemical and enzymatic methods. Most of these methods are capable of determining pyridoxine in the presence of other vitamins and complex systems in µg quantities. The development and applications of these methods in pharmaceutical and clinical analysis mostly during the last decade have been reviewed.

  11. The Mechanism of 2-Furaldehyde Formation from d-Xylose Dehydration in the Gas Phase. A Tandem Mass Spectrometric Study

    Science.gov (United States)

    Ricci, Andreina; Piccolella, Simona; Pepi, Federico; Garzoli, Stefania; Giacomello, Pierluigi

    2013-07-01

    The mechanism of reactions occurring in solution can be investigated also in the gas phase by suited mass spectrometric techniques, which allow to highlight fundamental mechanistic features independent of the influence of the medium and to clarifying controversial hypotheses proposed in solution studies. In this work, we report a gas-phase study performed by electrospray triple stage quadrupole mass spectrometry (ESI-TSQ/MS) on the dehydration of d-xylose, leading mainly to the formation of 2-furaldehyde (2-FA). It is generally known in carbohydrate chemistry that the thermal acid catalyzed dehydration of pentoses leads to the formation of 2-FA, but several aspects on the solution-phase mechanism are controversial. Here, gaseous reactant ions corresponding to protonated xylose molecules obtained from ESI of a solution containing d-xylose and ammonium acetate as protonating reagent were allowed to undergo collisionally activated decomposition (CAD) into the triple stage quadrupole analyzer. The product ion mass spectra of protonated xylose are characterized by the presence of ionic intermediates arising from xylose dehydration, which were structurally characterized by their fragmentation patterns. As expected, the xylose triple dehydration leads to the formation of the ion at m/z 97, corresponding to protonated 2-FA. On the basis of mass spectrometric evidences, we demonstrated that in the gas phase, the formation of 2-FA involves protonation at the OH group bound to the C1 atom of the sugar, the first ionic intermediate being characterized by a cyclic structure. Finally, energy resolved product ion mass spectra allowed to obtain information on the energetic features of the d-xylose→2-FA conversion.

  12. Mass spectrometric identification of proteins that interact through specific domains of the poly(A) binding protein.

    Science.gov (United States)

    Richardson, Roy; Denis, Clyde L; Zhang, Chongxu; Nielsen, Maria E O; Chiang, Yueh-Chin; Kierkegaard, Morten; Wang, Xin; Lee, Darren J; Andersen, Jens S; Yao, Gang

    2012-09-01

    Poly(A) binding protein (PAB1) is involved in a number of RNA metabolic functions in eukaryotic cells and correspondingly is suggested to associate with a number of proteins. We have used mass spectrometric analysis to identify 55 non-ribosomal proteins that specifically interact with PAB1 from Saccharomyces cerevisiae. Because many of these factors may associate only indirectly with PAB1 by being components of the PAB1-mRNP structure, we additionally conducted mass spectrometric analyses on seven metabolically defined PAB1 deletion derivatives to delimit the interactions between these proteins and PAB1. These latter analyses identified 13 proteins whose associations with PAB1 were reduced by deleting one or another of PAB1's defined domains. Included in this list of 13 proteins were the translation initiation factors eIF4G1 and eIF4G2, translation termination factor eRF3, and PBP2, all of whose previously known direct interactions with specific PAB1 domains were either confirmed, delimited, or extended. The remaining nine proteins that interacted through a specific PAB1 domain were CBF5, SLF1, UPF1, CBC1, SSD1, NOP77, yGR250c, NAB6, and GBP2. In further study, UPF1, involved in nonsense-mediated decay, was confirmed to interact with PAB1 through the RRM1 domain. We additionally established that while the RRM1 domain of PAB1 was required for UPF1-induced acceleration of deadenylation during nonsense-mediated decay, it was not required for the more critical step of acceleration of mRNA decapping. These results begin to identify the proteins most likely to interact with PAB1 and the domains of PAB1 through which these contacts are made.

  13. Development and validation of analytical methods for monomeric and oligomeric migrants from nylon 12 packaging materials.

    NARCIS (Netherlands)

    Stoffers, N.H.; Brandl, F.; Linssen, J.P.H.; Franz, R.

    2003-01-01

    Analytical methods for the determination of laurolactam-the monomer of nylon 12-as well as the cyclic dimer and trimer were established. High performance liquid chromatography using ultraviolet (HPLC-UV) and mass spectrometric detection (HPLC-MS) were both found suitable to identify and quantify mon

  14. NASVD and MNF techniques and your application noise reduction in gamma-ray spectrometric data; As tecnicas NASVD e MNF e sua aplicacao na reducao de ruidos em dados gamaespectrometricos

    Energy Technology Data Exchange (ETDEWEB)

    Cavallaro, Francisco de Assis, E-mail: assisfc@yahoo.com.br, E-mail: assis@agp-la.org [Departamento de Geologia Sedimentar e Ambiental, DGSA, Instituto de Geociencias, IG, Universidade de Sao Paulo, SP (Brazil); AGPLA, AeroGeoPhysica Latinoamerica, Sao Paulo, SP (Brazil); Portugal, Rodrigo S.; Bizuti, Ariathemis M., E-mail: portugal@ige.unicamp.br, E-mail: ambizuti@ige.unicamp.br [Departamento de Geologia e Recursos Naturais, DGRN, Instituto de Geociencias, IG, Universidade Estadual de Campinas, SP (Brazil); Silva, Adalene M., E-mail: adalene@unb.br [Universidade de Brasilia (UnB), DF (Brazil). Inst. de Geociencias. Dept. de Geoquimica e Recursos Minerais (GRM)

    2009-04-15

    The radioactive decay is a random process, and the measurement precision is ruled by statistical laws. The counting ratios of the profiles are always noisy when analyzed for short periods, such as one second per measurement. Corrections made at the end of conventional processing in the airborne gamma-ray spectrometric method data are not enough to remove and minimize, or even reduce considerably, the spectrum's originated noise. Two statistic methods that act locally in collected data, in the spectrum domain, have been suggested by literature to remove such remaining noises, the Noise-Adjusted Singular Value Decomposition - NASVD and Maximum Noise Fraction - MNF. These methods produce a significantly noise reduction. In this work both methods were applied in an area comprehended by two blocks, I and II, of the airborne survey that covers the west area of Mineral Province of Tapajos between Para and Amazon states. The filtered and non-filtered data with the NASVD and MNF techniques were processed with the Lasa's parameters. The comparison of results between maps and profiles shows that both methods are valuable, since there was resolution gain in these products. (author)

  15. Simultaneous analysis of multiple lipid oxidation products in vivo by liquid chromatographic-mass spectrometry (LC-MS).

    Science.gov (United States)

    Yin, Huiyong; Davis, Todd; Porter, Ned A

    2010-01-01

    Free radical-induced oxidation of polyunsaturated fatty acid (PUFAs) has been linked to a number of human diseases including atherosclerosis and neurodegenerative disorders. Oxidation of PUFAs generates hydroperoxides and cyclic peroxides that are reduced to lipid alcohol, such as hydroxyeicosatetraenoic acid (HETEs), and isoprostanes (IsoPs) respectively. The IsoPs are isomers of prostaglandins that are generated from autoxidation of arachidonic acid (C20:4). Quantification of F(2)-IsoPs has been regarded as the "gold standard" to assess oxidative stress status in various human diseases. We herein report the protocol of analyzing HETEs and F(2)-IsoPs using a triple quadrupole mass spectrometer coupled to reverse phase liquid chromatography. The selected reaction monitoring (SRM) mode selects the parent ion of interest in the first Quad (m/z 319 for HETE and m/z 353 for F(2)-IsoPs) and fragments it in the second while an ion characteristic of the analyte of interest is monitored in the third Quad. This highly selective technique permits the simultaneous analysis of multiple oxidation products such as the HETEs and F(2)-IsoPs. This LC-MS technique can be applied to study the free radical oxidation mechanism in vitro and assess the oxidative stress status in biological tissues and fluids.

  16. Field-portable Gas Chromatograph Mass Spectrometer (GC-MS) Unit for Semi-volatile Compound Analysis in Groundwater

    Science.gov (United States)

    2011-09-01

    and safety plan HBV Hepatitis B virus HIV Human Immunodeficiency Virus HPLC High Performance Liquid Chromatography HSO Health and Safety...and Space Administration (NASA). 2007. Arctic Mars Analog Svalbard Exedition (AMASE) Svalbard, Norway , August 12-26 2007. Pennington, J. C., R

  17. Biotransformation of 17-alkylsteroids in the equine: gas chromatographic-mass spectral identification of ten intermediate metabolites of methyltestosterone.

    Science.gov (United States)

    Stanley, S M; Smith, L; Rodgers, J P

    1997-03-01

    The metabolism of the orally active anabolic steroid methyltestosterone in the equine was investigated by administration of the drug along with a tritiated radiolabel tracer. In this study some of the metabolites were identified and a radio immunoassay screen and immunoaffinity chromatography gel for methyltestosterone were also evaluated. Pathway intermediates, in particular the 17-methylandrostanediols, were studied to gain an insight into the most likely stereochemistry of the major metabolites. The predominant phase I biotransformations involve reduction of the A ring 3-oxo and 4-ene groups to yield predominantly 3 beta-hydroxy-5 alpha-androstane products and hydroxylation of the steroid nucleus at several positions. Epimerisation of the 17 alpha-methyl group also occurred. Ten steroids could be positively identified by comparison with authentic reference materials and many other triol, tetrol and pentols were also observed. Phase II metabolites and sulphate conjugates in particular, were common.

  18. Quantitative determination of N-[trans-2-(dimethylamino)-cyclopentyl]-N-(3',4'-dichlorophenyl)propan amide, its 2H5-labeled analogue and their N-dealkylated metabolites in dog serum by capillary gas chromatography-mass spectrometry.

    Science.gov (United States)

    Theis, D L; Halstead, G W; Capponi, V J; Roach, B L; Robins, R H

    1986-03-07

    This paper describes the development of a capillary gas chromatographic--mass spectrometric method for the determination of N-[trans-2-(dimethylamino)cyclopentyl]-N-(3',4'-dichlorophenyl)propan amide and its metabolites in serum. The method utilizes an automated sample preparation whereby drug, metabolites and internal standard are extracted from polar serum components by adsorption chromatography onto an XAD-type resin. The N-demethylated metabolites are derivatized by acetylation prior to chromatography. Detection is by mass spectrometry with chemical ionization. This method was utilized to determine levels of unlabeled and pentadeuterated drug and their respective metabolites in canine serum after oral co-administration. No significant kinetic isotope effects were observed for either absorption or metabolism.

  19. Determination of Low Concentrations of Acetochlor in Water by Automated Solid-Phase Extraction and Gas Chromatography with Mass-Selective Detection

    Science.gov (United States)

    Lindley, C.E.; Stewart, J.T.; Sandstrom, M.W.

    1996-01-01

    A sensitive and reliable gas chromatographic/mass spectrometric (GC/MS) method for determining acetochlor in environmental water samples was developed. The method involves automated extraction of the herbicide from a filtered 1 L water sample through a C18 solid-phase extraction column, elution from the column with hexane-isopropyl alcohol (3 + 1), and concentration of the extract with nitrogen gas. The herbicide is quantitated by capillary/column GC/MS with selected-ion monitoring of 3 characteristic ions. The single-operator method detection limit for reagent water samples is 0.0015 ??g/L. Mean recoveries ranged from about 92 to 115% for 3 water matrixes fortified at 0.05 and 0.5 ??g/L. Average single-operator precision, over the course of 1 week, was better than 5%.

  20. Extraction and Characterization of Chemical Compounds in Coelaenomenodera elaeidis (Coleoptera: Chrysomelidae)

    Science.gov (United States)

    To elucidate the characterization of probable pheromone chemical compounds in Coelaenomenodera elaeidis Mlk., volatile samples were collected and subjected to gas chromatographic-mass spectrometric analyses. These compounds were contained in active fractions: Butylated hydroxytoluene (C15H24O); 4, 4...

  1. The similarity of chemical structures of soluble aliphatic polyaldehyde and insoluble algaenan in the green microalga Botryococcus braunii race A as revealed by analytical pyrolysis

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Gelin, F.; Leeuw, J.W. de; Derenne, S.; Largeau, C.; Metzger, P.

    1994-01-01

    Curie point pyrolysis-gas chromatographic-mass spectrometric studies of a recently isolated CHCl3-soluble aliphatic polyaldehyde, and of an insoluble biopolymer termed Bb(A) algaenan, of the green microalga Botryococcus braunii (race A) were performed to determine the structural relationships betwee

  2. Capillary liquid chromatography using laser-based and mass spectrometric detection. Final technical progress report, September 1, 1989--January 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Sepaniak, M.J.; Cook, K.D.

    1992-09-01

    In the years following the 1986 seminal paper (J. Chromatogr. Sci., 24, 347-352) describing modern capillary zone electrophoresis (CZE), the prominence of capillary electrokinetic separation techniques has grown. A related electrochromatographic technique is micellar electrokinetic capillary chromatography (MECC). This report presents a brief synopsis of research efforts during the current 3-year period. In addition to a description of analytical separations-based research, results of efforts to develop and expand spectrometric detection for the techniques is reviewed. Laser fluorometric detection schemes have been successfully advanced. Mass spectrometric research was less fruitful, largely owing to personnel limitations. A regenerable fiber optic sensor was developed that can be used to remotely monitor chemical carcinogens, etc. (DLC)

  3. Generic solid phase extraction-liquid chromatography-tandem mass spectrometry method for fast determination of drugs in biological fluids

    NARCIS (Netherlands)

    Schellen, A.; Ooms, B.; Lagemaat, D. van de; Vreeken, R.; Dongen, W.D. van

    2003-01-01

    A generic method was developed for the fast determination of a wide range of drugs in serum or plasma. The methodology comprises generic solid-phase extraction, on-line coupled to gradient HPLC with tandem mass spectrometric detection (SPE-LC-MS/MS). The individual components of the SPE-LC-MS/MS sys

  4. Combining Mass Spectrometric Metabolic Profiling with Genomic Analysis: A Powerful Approach for Discovering Natural Products from Cyanobacteria.

    Science.gov (United States)

    Kleigrewe, Karin; Almaliti, Jehad; Tian, Isaac Yuheng; Kinnel, Robin B; Korobeynikov, Anton; Monroe, Emily A; Duggan, Brendan M; Di Marzo, Vincenzo; Sherman, David H; Dorrestein, Pieter C; Gerwick, Lena; Gerwick, William H

    2015-07-24

    An innovative approach was developed for the discovery of new natural products by combining mass spectrometric metabolic profiling with genomic analysis and resulted in the discovery of the columbamides, a new class of di- and trichlorinated acyl amides with cannabinomimetic activity. Three species of cultured marine cyanobacteria, Moorea producens 3L, Moorea producens JHB, and Moorea bouillonii PNG, were subjected to genome sequencing and analysis for their recognizable biosynthetic pathways, and this information was then compared with their respective metabolomes as detected by MS profiling. By genome analysis, a presumed regulatory domain was identified upstream of several previously described biosynthetic gene clusters in two of these cyanobacteria, M. producens 3L and M. producens JHB. A similar regulatory domain was identified in the M. bouillonii PNG genome, and a corresponding downstream biosynthetic gene cluster was located and carefully analyzed. Subsequently, MS-based molecular networking identified a series of candidate products, and these were isolated and their structures rigorously established. On the basis of their distinctive acyl amide structure, the most prevalent metabolite was evaluated for cannabinomimetic properties and found to be moderate affinity ligands for CB1.

  5. Mass Spectrometric-Based Selected Reaction Monitoring of Protein Phosphorylation during Symbiotic Signaling in the Model Legume, Medicago truncatula.

    Directory of Open Access Journals (Sweden)

    Lori K Van Ness

    Full Text Available Unlike the major cereal crops corn, rice, and wheat, leguminous plants such as soybean and alfalfa can meet their nitrogen requirement via endosymbiotic associations with soil bacteria. The establishment of this symbiosis is a complex process playing out over several weeks and is facilitated by the exchange of chemical signals between these partners from different kingdoms. Several plant components that are involved in this signaling pathway have been identified, but there is still a great deal of uncertainty regarding the early events in symbiotic signaling, i.e., within the first minutes and hours after the rhizobial signals (Nod factors are perceived at the plant plasma membrane. The presence of several protein kinases in this pathway suggests a mechanism of signal transduction via posttranslational modification of proteins in which phosphate is added to the hydroxyl groups of serine, threonine and tyrosine amino acid side chains. To monitor the phosphorylation dynamics and complement our previous untargeted 'discovery' approach, we report here the results of experiments using a targeted mass spectrometric technique, Selected Reaction Monitoring (SRM that enables the quantification of phosphorylation targets with great sensitivity and precision. Using this approach, we confirm a rapid change in the level of phosphorylation in 4 phosphosites of at least 4 plant phosphoproteins that have not been previously characterized. This detailed analysis reveals aspects of the symbiotic signaling mechanism in legumes that, in the long term, will inform efforts to engineer this nitrogen-fixing symbiosis in important non-legume crops such as rice, wheat and corn.

  6. Mass Spectrometric-Based Selected Reaction Monitoring of Protein Phosphorylation during Symbiotic Signaling in the Model Legume, Medicago truncatula.

    Science.gov (United States)

    Van Ness, Lori K; Jayaraman, Dhileepkumar; Maeda, Junko; Barrett-Wilt, Gregory A; Sussman, Michael R; Ané, Jean-Michel

    2016-01-01

    Unlike the major cereal crops corn, rice, and wheat, leguminous plants such as soybean and alfalfa can meet their nitrogen requirement via endosymbiotic associations with soil bacteria. The establishment of this symbiosis is a complex process playing out over several weeks and is facilitated by the exchange of chemical signals between these partners from different kingdoms. Several plant components that are involved in this signaling pathway have been identified, but there is still a great deal of uncertainty regarding the early events in symbiotic signaling, i.e., within the first minutes and hours after the rhizobial signals (Nod factors) are perceived at the plant plasma membrane. The presence of several protein kinases in this pathway suggests a mechanism of signal transduction via posttranslational modification of proteins in which phosphate is added to the hydroxyl groups of serine, threonine and tyrosine amino acid side chains. To monitor the phosphorylation dynamics and complement our previous untargeted 'discovery' approach, we report here the results of experiments using a targeted mass spectrometric technique, Selected Reaction Monitoring (SRM) that enables the quantification of phosphorylation targets with great sensitivity and precision. Using this approach, we confirm a rapid change in the level of phosphorylation in 4 phosphosites of at least 4 plant phosphoproteins that have not been previously characterized. This detailed analysis reveals aspects of the symbiotic signaling mechanism in legumes that, in the long term, will inform efforts to engineer this nitrogen-fixing symbiosis in important non-legume crops such as rice, wheat and corn.

  7. Processing and Assessment of Spectrometric, Stereoscopic Imagery Collected Using a Lightweight UAV Spectral Camera for Precision Agriculture

    Directory of Open Access Journals (Sweden)

    Jussi Mäkynen

    2013-10-01

    Full Text Available Imaging using lightweight, unmanned airborne vehicles (UAVs is one of the most rapidly developing fields in remote sensing technology. The new, tunable, Fabry-Perot interferometer-based (FPI spectral camera, which weighs less than 700 g, makes it possible to collect spectrometric image blocks with stereoscopic overlaps using light-weight UAV platforms. This new technology is highly relevant, because it opens up new possibilities for measuring and monitoring the environment, which is becoming increasingly important for many environmental challenges. Our objectives were to investigate the processing and use of this new type of image data in precision agriculture. We developed the entire processing chain from raw images up to georeferenced reflectance images, digital surface models and biomass estimates. The processing integrates photogrammetric and quantitative remote sensing approaches. We carried out an empirical assessment using FPI spectral imagery collected at an agricultural wheat test site in the summer of 2012. Poor weather conditions during the campaign complicated the data processing, but this is one of the challenges that are faced in operational applications. The results indicated that the camera performed consistently and that the data processing was consistent, as well. During the agricultural experiments, promising results were obtained for biomass estimation when the spectral data was used and when an appropriate radiometric correction was applied to the data. Our results showed that the new FPI technology has a great potential in precision agriculture and indicated many possible future research topics.

  8. Ultraviolet irradiation-induced substitution of fluorine with hydroxyl radical for mass spectrometric analysis of perfluorooctane sulfonyl fluoride

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Peng; Tang, Xuemei; Huang, Lulu; Kang, Jie; Zhong, Hongying, E-mail: hyzhong@mail.ccnu.edu.cn

    2016-01-28

    A rapid and solvent free substitution reaction of a fluorine atom in perfluorooctane sulfonyl fluoride (PFOSF) with a hydroxyl radical is reported. Under irradiation of ultraviolet laser on semiconductor nanoparticles or metal surfaces, hydroxyl radicals can be generated through hole oxidization. Among all fluorine atoms of PFOSF, highly active hydroxyl radicals specifically substitute the fluorine of sulfonyl fluoride functional group. Resultant perfluorooctane sulfonic acid is further ionized through capture of photo-generated electrons that switch the neutral molecules to negatively charged odd electron hypervalent ions. The unpaired electron subsequently initiates α O–H bond cleavage and produces perfluorooctane sulfonate negative ions. Hydroxyl radical substitution and molecular dissociation of PFOSF have been confirmed by masses with high accuracy and resolution. It has been applied to direct mass spectrometric imaging of PFOSF adsorbed on surfaces of plant leaves. - Highlights: • Ultraviolet irradiation on semiconductor nanoparticles produces electron–hole pairs. • Hole oxidization results in the formation of hydroxyl radicals. • Fluorine atoms of PFOSF can be specifically substituted with hydroxyl radicals. • Capture of photoelectrons causes dissociation and fragmentation. • Fragments are detected in negative ion mode.

  9. Comparison of extraction techniques and mass spectrometric ionization modes in the analysis of wine volatile carbonyls

    Energy Technology Data Exchange (ETDEWEB)

    Zapata, Julian; Mateo-Vivaracho, Laura; Cacho, Juan [Laboratory for Flavor Analysis and Enology, Institute of Engineering of Aragon, I3A, Department of Analytical Chemistry, Faculty of Sciences, University of Zaragoza, 50009 Zaragoza (Spain); Ferreira, Vicente, E-mail: vferre@unizar.es [Laboratory for Flavor Analysis and Enology, Institute of Engineering of Aragon, I3A, Department of Analytical Chemistry, Faculty of Sciences, University of Zaragoza, 50009 Zaragoza (Spain)

    2010-02-15

    This work presents a comparative study of the analytical characteristics of two methods for the analysis of carbonyl compounds in wine, both based on the derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA). In the first method derivatives are formed in the solid phase extraction (SPE) cartridge in which the analytes have been previously isolated, while in the second method derivatives are formed in a solid phase microextraction (SPME) fibre saturated with vapors of the reagent and exposed to the sample headspace. In both cases detection has been carried out by electron impact (EI) or negative chemical ionization (NCI) mass spectrometry. The possibility of determining haloanisols simultaneously has been also considered. The method based on SPE presents, in general, better analytical properties than the SPME one. Although linearity was satisfactory for both methods (R{sup 2} > 0.99), repeatability of the SPE method (RSD < 10%) was better than that obtained with SPME (9% < RSD < 20%). Detection limits obtained with EI are better for the SPE method except for trihaloanisols, while with NCI detection limits for both strategies are comparable, although the SPME strategy presents worse results for ketones and methional. Detection limits are always lower with NCI, being the improvement most notable for SPME. Recovery experiments show that in the case of SPE, uncertainties are lower than 12% in all cases, while with the SPME method the imprecision plus the existence of matrix effects make the global uncertainty to be higher than 15%.

  10. The Mass Spectrometric Ortho Effect Studied for All 209 PCB Congeners

    Science.gov (United States)

    A method for the determination of polychlorinated biphenyls (PCBs) in caulk was developed; with application to a set of caulk and window glazing material samples. This method was evaluated by analyzing a combination of 47 samples of caulk, glazing materials, and including quality...

  11. Analytical determination of virginiamycin drug residues in edible porcine tissues by LC-MS with confirmation by LC-MS/MS.

    Science.gov (United States)

    Boison, Joe; Lee, Stephen; Gedir, Ron

    2009-01-01

    A liquid chromatographic-mass spectrometric (LC-MS) method was developed and validated for the determination and confirmation of virginiamycin (VMY) M1 residues in porcine liver, kidney, and muscle tissues at concentrations > or =2 ng/g. Porcine liver, kidney, or muscle tissue is homogenized with methanol-acetonitrile. After centrifugation, the supernatant is diluted with phosphate buffer and cleaned up on a C18 solid-phase extraction cartridge. VMY in the eluate is partitioned into chloroform and the aqueous upper layer is removed by aspiration. After evaporating the chloroform in the residual mixture to dryness, the dried extract is reconstituted in mobile phase and VMY is quantified by LC-MS. Any samples eliciting quantifiable levels of VMY M1 (i.e., at concentrations > or =2 ng/g) are subjected to confirmatory analysis by LC-MSIMS. VMY S1, a minor component of the VMY complex, is monitored but not quantified or confirmed.

  12. Excretion of cannabinoids in urine after ingestion of cannabis seed oil.

    Science.gov (United States)

    Lehmann, T; Sager, F; Brenneisen, R

    1997-09-01

    Gas chromatographic-mass spectrometric (GC-MS) quantitation of 25 cannabis sed oils determined delta 9-tetrahydrocannabinol (THC) concentrations from 3 to 1500 micrograms/g oil. In a pilot study, the morning urine of six volunteers who had ingested 11 or 22 g of the oil, which contained the highest THC content (1500 micrograms/g), was collected for six days. The urine samples were screened by immunoassay, and the content of 11-nor-9-carboxy-delta 9-THC (THCCOOH) was determined by GC-MS. Urine samples were found cannabis positive for up to six days with THCCOOH-equivalent concentrations up to 243 ng/mL. by the Abuscreen OnLine immunoassay and THCCOOH contents from 5 to 431 ng/mL by the GC-MS method. All subjects reported THC-specific psychotropic effects.

  13. Chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solutions

    Energy Technology Data Exchange (ETDEWEB)

    1981-01-01

    The standard covers analytical procedures to determine compliance of nuclear-grade uranyl nitrate solution to specifications. The following methods are described in detail: uranium by ferrous sulfate reduction-potassium dichromate titrimetry and by ignition gravimetry; specific gravity by pycnometry; free acid by oxalate complexation; thorium by the Arsenazo(III) (photometric) method; chromium by the diphenylcarbazide (photometric) method; molybdenum by the thiocyanate (photometric) method; halogens separation by steam distillation; fluorine by specific ion electrode; halogen distillate analysis: chloride, bromide and iodide by amperometric microtitrimetry; bromine by the fluorescein (photometric) method; sulfate sulfur by (photometric) turbidimetry; phosphorus by the molybdenum blue (photometric) method; silicon by the molybdenum blue (photometric) method; carbon by persulfate oxidation-acid titrimetry; nonvolatile impurities by spectrography; volatile impurities by rotating-disk spark spectrography; boron by emission spectrography; impurity elements by spark source mass spectrography; isotopic composition by multiple filament surface-ionization mass spectrometry; uranium-232 by alpha spectrometry; total alpha activity by direct alpha counting; fission product activity by beta and gamma counting; entrained organic matter by infrared spectrophotometry. (JMT)

  14. Mass spectrometric quantification of salivary metanephrines-A study in healthy subjects

    NARCIS (Netherlands)

    Osinga, Thamara E.; Horst-Schrivers, van der Anouk N. A.; van Faassen, Martijn; Kerstens, Michiel N.; Dullaart, Robin P. F.; Pacak, Karel; Links, Thera P.; Kema, Ido P.

    2016-01-01

    Background: Determination of metanephrine (MN), normetanephrine (NMN), and 3-methoxytyramine (3-MT) in saliva may offer potential diagnostic advantages in diagnosing pheochromocytoma. Methods: In this preliminary study, we determined metanephrine concentrations in saliva of healthy subjects and the

  15. Gamma-spectrometric surveys in differentiated granites. II: the Joaquim Murtinho Granite in the Cunhaporanga Granitic Complex, Parana, SE Brazil; Levantamentos gamaespectrometricos em granitos diferenciados. II: O exemplo do Granito Joaquim Murtinho, Complexo Granitico Cunhaporanga, Parana

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Francisco Jose Fonseca [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Dept. de Geologia. Lab. de Pesquisas em Geofisica Aplicada; Fruchting, Allan [Votorantim Metais, Sao Paulo, SP (Brazil)], e-mail: allan.fruchting@vmetais.com.br; Guimaraes, Gilson Burigo [Universidade Estadual de Ponta Grossa (UEPG), PR (Brazil). Dept. de Geociencias], e-mail: gburigo@ig.com.br; Alves, Luizemara Soares [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil)], e-mail: luizemara@petrobras.com.br; Martin, Victor Miguel Oliveira; Ulbrich, Horstpeter Herberto Gustavo Jose [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Geociencias. Dept. de Mineralogia e Geotectonica], e-mail: vicmartin6@ig.com.br, e-mail: hulbrich@usp.br

    2009-07-01

    Detailed mapping at the NW corner of the large Neo proterozoic Cunhaporanga Granitic Complex (CGC), Parana state, SE Brazil, redefined the Joaquim Murtinho Granite (JMG), a late intrusion in CGC with an exposed area of about 10 km{sup 2}, made up mainly by evolved 'alaskites' (alkali-feldspar leuco granites). This unit is in tectonic contact with the Neoproterozoic-Eocambrian volcano-sedimentary Castro Group, to the W, and is intrusive into other less evolved granitic units of the CGC to the E. Petrographically, JMG shows mainly mesoperthite and quartz, with subordinate amounts of altered micas and some accessory phases, mainly zircon. The equi to inequigranular granites are usually deformed with cataclastic textures, are often brecciated, and may have miarolitic structures. Formation of late albite, sericite, carbonate and hematite was caused by deuteric and hydrothermal alteration. A gamma-ray spectrometric survey at 231 stations which measured total counts (TC), Ueq K%, eU ppm and eTh ppm was used to construct several direct and derived maps. Compared to neighboring units the JMG has significant anomalies, especially in the TC, %K, eTh and eU maps, although the differences are less obvious in some derived maps. These evolved granites are enriched in these three elements. Geochemical behavior of K, Th and U is used to analyse the results observed in maps. Enhanced weathering under a subtropical climate with moderate to high average temperatures and heavy rainfall affects mainly feldspars and biotite, and may also destabilize most U and Th-bearing accessory phases. Th is most likely retained in restite minerals in soils, being relatively immobile, while part of U may migrate as uranyl ion in oxidizing media. K is especially affected by feldspar alteration to K-free clays (mainly kaolinite), and may be completely leached. Gamma-ray spectrometric methods are valid tools to study facies in granitic rocks, especially in those that are enriched in K, Th and U

  16. Analysis of small carbohydrates in several bioactive botanicals by gas chromatography with mass spectrometry and liquid chromatography with tandem mass spectrometry.

    Science.gov (United States)

    Moldoveanu, Serban; Scott, Wayne; Zhu, Jeff

    2015-11-01

    Bioactive botanicals contain natural compounds with specific biological activity, such as antibacterial, antioxidant, immune stimulating, and taste improving. A full characterization of the chemical composition of these botanicals is frequently necessary. A study of small carbohydrates from the plant materials of 18 bioactive botanicals is further described. The study presents the identification of the carbohydrate using a gas chromatographic-mass spectrometric analysis that allows detection of molecules as large as maltotetraose, after changing them into trimethylsilyl derivatives. A number of carbohydrates in the plant (fructose, glucose, mannose, sucrose, maltose, xylose, sorbitol, and myo-, chiro-, and scyllo-inositols) were quantitated using a novel liquid chromatography with tandem mass spectrometric technique. Both techniques involved new method developments. The gas chromatography with mass spectrometric analysis involved derivatization and separation on a Rxi(®)-5Sil MS column with H2 as a carrier gas. The liquid chromatographic separation was obtained using a hydrophilic interaction type column, YMC-PAC Polyamine II. The tandem mass spectrometer used an electrospray ionization source in multiple reaction monitoring positive ion mode with the detection of the adducts of the carbohydrates with Cs(+) ions. The validated quantitative procedure showed excellent precision and accuracy allowing the analysis in a wide range of concentrations of the analytes.

  17. Calibration of mass spectrometric peptide mass fingerprint data without specific external or internal calibrants

    Directory of Open Access Journals (Sweden)

    Lalowski Maciej

    2005-08-01

    Full Text Available Abstract Background Peptide Mass Fingerprinting (PMF is a widely used mass spectrometry (MS method of analysis of proteins and peptides. It relies on the comparison between experimentally determined and theoretical mass spectra. The PMF process requires calibration, usually performed with external or internal calibrants of known molecular masses. Results We have introduced two novel MS calibration methods. The first method utilises the local similarity of peptide maps generated after separation of complex protein samples by two-dimensional gel electrophoresis. It computes a multiple peak-list alignment of the data set using a modified Minimum Spanning Tree (MST algorithm. The second method exploits the idea that hundreds of MS samples are measured in parallel on one sample support. It improves the calibration coefficients by applying a two-dimensional Thin Plate Splines (TPS smoothing algorithm. We studied the novel calibration methods utilising data generated by three different MALDI-TOF-MS instruments. We demonstrate that a PMF data set can be calibrated without resorting to external or relying on widely occurring internal calibrants. The methods developed here were implemented in R and are part of the BioConductor package mscalib available from http://www.bioconductor.org. Conclusion The MST calibration algorithm is well suited to calibrate MS spectra of protein samples resulting from two-dimensional gel electrophoretic separation. The TPS based calibration algorithm might be used to correct systematic mass measurement errors observed for large MS sample supports. As compared to other methods, our combined MS spectra calibration strategy increases the peptide/protein identification rate by an additional 5 – 15%.

  18. MALDI-TOF mass spectrometric determination of eight benzodiazepines with two of their metabolites in blood.

    Science.gov (United States)

    Nozawa, Hideki; Minakata, Kayoko; Yamagishi, Itaru; Hasegawa, Koutaro; Wurita, Amin; Gonmori, Kunio; Suzuki, Osamu; Watanabe, Kanako

    2015-05-01

    A rapid and sensitive method was developed for the determination of benzodiazepines and benzodiazepine-like substances (BZDs) by matrix-assisted laser desorption ionization (MALDI)-time-of-flight (TOF)-mass spectrometry (MS). In this method, α-cyano-4-hydroxy cinnamic acid was used as the matrix to assist the ionization of BZDs. Determination of 8 BZDs (with two of their metabolites) belonging to top 12 medical drugs detected in poisonous cases in Japan, was performed using diazepam-d5 as the internal standard. The limit of detection of zolpidem was 0.07ng/ml with its quantification range of 0.2-20ng/ml in blood, in the best case, and the limit of detection of flunitrazepam was 2ng/ml with its quantification range of 6-200ng/ml in blood, in the worst case. The spectra of zopiclone in MALDI-MS and MS/MS were different from those in electrospray ionization MS and MS/MS. Present method provides a simple and high throughput method for the screening of these BZDs using only 20μl of blood. The developed method was successfully used for the determination of BZDs in biological fluids obtained from two victims.

  19. Preprocessing of Tandem Mass Spectrometric Data Based on Decision Tree Classification

    Institute of Scientific and Technical Information of China (English)

    Jing-Fen Zhang; Si-Min He; Jin-Jin Cai; Xing-Jun Cao; Rui-Xiang Sun; Yan Fu; Rong Zeng; Wen Gao

    2005-01-01

    In this study, we present a preprocessing method for quadrupole time-of-flight(Q-TOF) tandem mass spectra to increase the accuracy of database searching for peptide (protein) identification. Based on the natural isotopic information inherent in tandem mass spectra, we construct a decision tree after feature selection to classify the noise and ion peaks in tandem spectra. Furthermore, we recognize overlapping peaks to find the monoisotopic masses of ions for the following identification process. The experimental results show that this preprocessing method increases the search speed and the reliability of peptide identification.

  20. A rapid method to authenticate vegetable oils through surface-enhanced Raman scattering

    Science.gov (United States)

    Lv, Ming Yang; Zhang, Xin; Ren, Hai Rui; Liu, Luo; Zhao, Yong Mei; Wang, Zheng; Wu, Zheng Long; Liu, Li Min; Xu, Hai Jun

    2016-03-01

    Vegetable oils are essential in our daily diet. Among various vegetable oils, the major difference lies in the composition of fatty acids, including unsaturated fatty acids (USFA) and saturated fatty acids (SFA). USFA include oleic acid (OA), linoleic acid (LA), and α-linolenic acid (ALA), while SFA are mainly palmitic acid (PA). In this study, the most typical and abundant USFA present with PA in vegetable oils were quantified. More importantly, certain proportional relationships between the integrated intensities of peaks centered at 1656 cm-1 (S1656) in the surface-enhanced Raman scattering spectra of different USFA were confirmed. Therefore, the LA or ALA content could be converted into an equivalent virtual OA content enabling the characterization of the USFA content in vegetable oils using the equivalent total OA content. In combination with the S1656 of pure OA and using peanut, sesame, and soybean oils as examples, the ranges of S1656 corresponding to the National Standards of China were established to allow the rapid authentication of vegetable oils. Gas chromatograph-mass spectrometer analyses verified the accuracy of the method, with relative errors of less than 5%. Moreover, this method can be extended to other detection fields, such as diseases.

  1. Gas chromatography-mass spectrometric assay for propofol in cerebrospinal fluid of traumatic brain patients

    NARCIS (Netherlands)

    Peeters, Mariska Y. M.; Kuiper, Hiltjo; Greijdanus, Ben; van der Naalt, Joukje; Knibbe, Catherijne A. J.; Uges, Donald R. A.

    2007-01-01

    A sensitive gas chromatography-mass spectrometry method for measuring propofol in cerebrospinal fluid is described, validated and applied to four patients after traumatic brain injury. The limit of quantitation was 2 mu g/L using a volume of 0.5 mL. The inter- and intra-assay coefficients of variati

  2. An indirect atomic absorption spectrometric determination of ciprofloxacin, amoxycillin and diclofenac sodium in pharmaceutical formulations

    Directory of Open Access Journals (Sweden)

    MAHMOUD MOHAMED ISSA

    2008-05-01

    Full Text Available A highly sensitive indirect atomic absorption spectrophotometric (AAS method has been developed for the determination of very low concentrations of ciprofloxacin, amoxycillin and diclofenac sodium. The method is based on the oxidation of these drugs with iron(III. The excess of iron(III was extracted into diethyl ether and then the iron(II in the aqueous layer was aspirated into an air–acetylene flame and determined by AAS. The linear concentration ranges were 25–400, 50–500 and 60–600 ng ml-1 for ciprofloxacin, amoxycillin and diclofenac sodium, respectively. The results were statistically compared with the official method using t- and f-test at p < 0.05. There were insignificant interferences from most of the excipients present. The intra- and inter-day assay coefficients of variation were less than 6.1 % and the recoveries ranged from 95 to 103 %. The method was applied for the analysis of these drug substances in their commercial pharmaceutical formulations.

  3. Research on Calibration Transfer across Infrared Spectrometric Instruments for Fast Evaluation of Crude Oils

    Institute of Scientific and Technical Information of China (English)

    Li Jingyan; Chu Xiaoli; Tian Songbai

    2015-01-01

    The spectral analysis method is suitable for the process control and the process analysis such as the fast evalua-tion of crude oils. In this study, model transfer between the same type of spectrometer and different type of spectrometers was discussed respectively, and the results have shown that the transfer of calibration model can satisfy the demand of rapid analysis.

  4. Matrix-free UV-laser desorption/ionization (LDI) mass spectrometric imaging at the single-cell level: distribution of secondary metabolites of Arabidopsis thaliana and Hypericum species.

    Science.gov (United States)

    Hölscher, Dirk; Shroff, Rohit; Knop, Katrin; Gottschaldt, Michael; Crecelius, Anna; Schneider, Bernd; Heckel, David G; Schubert, Ulrich S; Svatos, Ales

    2009-12-01

    The present paper describes matrix-free laser desorption/ionisation mass spectrometric imaging (LDI-MSI) of highly localized UV-absorbing secondary metabolites in plant tissues at single-cell resolution. The scope and limitations of the method are discussed with regard to plants of the genus Hypericum. Naphthodianthrones such as hypericin and pseudohypericin are traceable in dark glands on Hypericum leaves, placenta, stamens and styli; biflavonoids are also traceable in the pollen of this important phytomedical plant. The highest spatial resolution achieved, 10 microm, was much higher than that achieved by commonly used matrix-assisted laser desorption/ionization (MALDI) imaging protocols. The data from imaging experiments were supported by independent LDI-TOF/MS analysis of cryo-sectioned, laser-microdissected and freshly cut plant material. The results confirmed the suitability of combining laser microdissection (LMD) and LDI-TOF/MS or LDI-MSI to analyse localized plant secondary metabolites. Furthermore, Arabidopsis thaliana was analysed to demonstrate the feasibility of LDI-MSI for other commonly occurring compounds such as flavonoids. The organ-specific distribution of kaempferol, quercetin and isorhamnetin, and their glycosides, was imaged at the cellular level.

  5. Advanced x-ray spectrometric techniques for characterization of nuclear materials: An overview of recent laboratory activities

    Science.gov (United States)

    Misra, N. L.

    2014-11-01

    Advancements in x-ray spectrometric techniques at different stages have made this technique suitable for characterization of nuclear materials with respect to trace/major element determinations and compositional uniformity studies. The two important features of total reflection x-ray fluorescence spectrometry: 1) requirement of very small amount of sample in ng level 2) multielement analytical capability, in addition to other features, make this technique very much suitable to nuclear materials characterization as most of the nuclear materials are radioactive and the radioactive waste generated and radiation hazards to the operator are minimum when such low amount of sample is used. Similarly advanced features of energy dispersive x-ray fluorescence e.g. better geometry for high flux, reduction in background due to application of radiation filters have made the measurements of samples sealed inside thin alkathene/PVC covers possible with good sensitivity. This approach avoids putting the instrument inside a glove box for measuring radioactive samples and makes the operation/maintenance of the instrument and analysis of the samples possible in easy and fast manner. This approach has been used for major element determinations in mixed uranium-plutonium samples. Similarly μ-XRF with brilliant and micro-focused excitation sources can be used for compositional uniformity study of reactor fuel pellets. A μ-XRF study using synchrotron light source has been made to assess the compositional uniformity of mixed uranium-thorium oxide pellets produced by different processes. This approach is simple as it does not involve any sample preparation and is non-destructive. A brief summary of such activities carried out in our laboratory in past as well as ongoing and planned for the future have been discussed in the present manuscript.

  6. FiD: a software for ab initio structural identification of product ions from tandem mass spectrometric data.

    Science.gov (United States)

    Heinonen, Markus; Rantanen, Ari; Mielikäinen, Taneli; Kokkonen, Juha; Kiuru, Jari; Ketola, Raimo A; Rousu, Juho

    2008-10-01

    We present FiD (Fragment iDentificator), a software tool for the structural identification of product ions produced with tandem mass spectrometric measurement of low molecular weight organic compounds. Tandem mass spectrometry (MS/MS) has proven to be an indispensable tool in modern, cell-wide metabolomics and fluxomics studies. In such studies, the structural information of the MS(n) product ions is usually needed in the downstream analysis of the measurement data. The manual identification of the structures of MS(n) product ions is, however, a nontrivial task requiring expertise, and calls for computer assistance. Commercial software tools, such as Mass Frontier and ACD/MS Fragmenter, rely on fragmentation rule databases for the identification of MS(n) product ions. FiD, on the other hand, conducts a combinatorial search over all possible fragmentation paths and outputs a ranked list of alternative structures. This gives the user an advantage in situations where the MS/MS data of compounds with less well-known fragmentation mechanisms are processed. FiD software implements two fragmentation models, the single-step model that ignores intermediate fragmentation states and the multi-step model, which allows for complex fragmentation pathways. The software works for MS/MS data produced both in positive- and negative-ion modes. The software has an easy-to-use graphical interface with built-in visualization capabilities for structures of product ions and fragmentation pathways. In our experiments involving amino acids and sugar-phosphates, often found, e.g., in the central carbon metabolism of yeasts, FiD software correctly predicted the structures of product ions on average in 85% of the cases. The FiD software is free for academic use and is available for download from www.cs.helsinki.fi/group/sysfys/software/fragid.

  7. High-resolution mass spectrometric identification and quantification of glucocorticoid compounds in various wastewaters in the Netherlands.

    Science.gov (United States)

    Schriks, Merijn; van Leerdam, Jan A; van der Linden, Sander C; van der Burg, Bart; van Wezel, Annemarie P; de Voogt, Pim

    2010-06-15

    In the past two decades much research effort has focused on the occurrence, effects, and risks of estrogenic compounds. However, increasing emissions of new emerging compounds may also affect the action of hormonal pathways other than the estrogenic hormonal axis. Recently, a suite of novel CALUX bioassays has become available that enables looking further than estrogenic effects only. By employing these bioassays, we recently showed high glucocorticogenic activity in wastewaters collected at various sites in The Netherlands. However, since bioassays provide an integrated biological response, the identity of the responsible biological compounds remained unknown. Therefore, our current objective was to elucidate the chemical composition of the wastewater extracts used in our previous study by means of LC-high-resolution Orbitrap MS/MS and to determine if the compounds quantified could account for the observed glucocorticoid responsive (GR) CALUX bioassay response. The mass spectrometric analysis revealed the presence of various glucocorticoids in the range of 13-1900 ng/L. In extracts of hospital wastewater-collected prior to sewage treatment-several glucocorticoids were identified (cortisol 275-301 ng/L, cortisone 381-472 ng/L, prednisone 117-545 ng/L, prednisolone 315-1918 ng/L, and triamcinolone acetonide 14-41 ng/L) which are used to treat a great number of human pathologies. A potency balance calculation based on the instrumental analyses and relative potencies (REPs) of the individual glucocorticoids supports the conclusion that triamcinolone acetonide (REP = 1.3), dexamethasone (REP = 1), and prednisolone (REP = 0.2) are the main contributors to the glucocorticogenic activity in the investigated wastewater extracts. The action of these compounds is concentration additive and the overall glucocorticogenic activity can be explained to a fairly large extent by their contribution.

  8. Targeted natural products discovery from marine cyanobacteria using combined phylogenetic and mass spectrometric evaluation.

    Science.gov (United States)

    Salvador-Reyes, Lilibeth A; Engene, Niclas; Paul, Valerie J; Luesch, Hendrik

    2015-03-27

    Combined phylogenetic and HPLC-MS-based natural products dereplication methods aimed at identifying cyanobacterial collections containing the potent cytotoxins largazole, dolastatin 10, and symplostatin 1 were developed. The profiling of the phylogeny, chemical space, and antiproliferative activity of cyanobacterial collections served to streamline the prioritization of samples for the discovery of new secondary metabolites. The dereplication methods highlighted the biosynthetic potential and combinatorial pharmacology employed by marine cyanobacteria. We found that largazole was always coproduced with dolastatin 10 or with symplostatin 1 and consequently tested combinations of these agents against colon cancer cells. Combinatorial regimens of largazole and dolastatin 10 aimed at curbing the growth of HCT116 cancer cells showed cooperative activity.

  9. Spectrometric determination of clinically relevant fatty acids in the blood serum

    Science.gov (United States)

    Kalinin, A. V.; Krasheninnikov, V. N.; Sviridov, A. P.; Titov, V. N.

    2016-12-01

    The content of fatty acid (FA) triglycerides in food and biological media is predicting traditionally using gas and liquid chromatographic methods. Named techniques aren't available for clinical labs due to their complexity. So, our objective was to develop the method and apparatus for rapid assay of a few clinically important FA as the saturated palmitic, mono unsaturated oleic and others in serum using near infrared spectrometer. As a result, the applicability of the FT spectrometer in the wavelength range of 0.9 -1.8 μ to analyze these FA in serum without sample preparation was confirmed. Besides, measurement specifications were determined and a correlations of the absorption spectra and contents of total triglycerides and cholesterol, palmitic, oleic, linoleic and arachidonic FA in serum were established

  10. Liquid chromatography/electrospray ionization mass spectrometric characterization of Harpagophytum in equine urine and plasma.

    Science.gov (United States)

    Colas, Cyril; Garcia, Patrice; Popot, Marie-Agnès; Bonnaire, Yves; Bouchonnet, Stéphane

    2006-01-01

    A method has been developed for the analysis and characterization in equine urine and plasma of iridoid glycosides: harpagide, harpagoside and 8-para-coumaroyl harpagide, which are the main active principles of Harpagophytum, a plant with antiinflammatory properties. The method involves liquid chromatography coupled with positive electrospray ionization mass spectrometry. The addition of sodium or lithium chloride instead of formic acid in the eluting solvent has been studied in order to enhance the signal and to modify the ion's internal energy. Fragmentation pathways and associated patterns are proposed for each analyte. A comparison of three types of mass spectrometer: a 3D ion trap, a triple quadrupole and a linear ion trap, has been conducted. The 3D ion trap was selected for drug screening analysis whereas the linear ion trap was retained for identification and quantitation analysis.

  11. Laser Raman spectrometric determination of oxy-anions in nuclear waste materials

    Energy Technology Data Exchange (ETDEWEB)

    Miller, A.G.

    1977-03-01

    Oxy-anions in complex nuclear process-waste materials are being determined by laser Raman spectrometry (LRS). The double internal-standard technique developed by Marston is applied to the simultaneous determination of up to x anions in alkaline solutions. The method of Marston has been extended to solutions prepared from the solids formed in nuclear waste storage tanks. As many as six anions, aluminate, chromate, nitrate, nitrite, phosphate, and sulfate, are simultaneously determined in about one hour. Carbonate may also be determined, but in the presence of the prevalent nitrate, a chemical separation is required. Individual methods have been relegated to a secondary status due to the many advantages of LRS. Advantages such as small sample size, speed of analysis, accuracy, and specificity will be discussed. The typical precision obtained for analyses in high concentration is around five percent relative standard deviation.

  12. Ion exchange separation of chromium from natural water matrix for stable isotope mass spectrometric analysis

    Science.gov (United States)

    Ball, J.W.; Bassett, R.L.

    2000-01-01

    A method has been developed for separating the Cr dissolved in natural water from matrix elements and determination of its stable isotope ratios using solid-source thermal-ionization mass spectrometry (TIMS). The separation method takes advantage of the existence of the oxidized form of Cr as an oxyanion to separate it from interfering cations using anion-exchange chromatography, and of the reduced form of Cr as a positively charged ion to separate it from interfering anions such as sulfate. Subsequent processing of the separated sample eliminates residual organic material for application to a solid source filament. Ratios for 53Cr/52Cr for National Institute of Standards and Technology Standard Reference Material 979 can be measured using the silica gel-boric acid technique with a filament-to-filament standard deviation in the mean 53Cr/52Cr ratio for 50 replicates of 0.00005 or less. (C) 2000 Elsevier Science B.V. All rights reserved.

  13. Me-BTABr reagent in cloud point extraction for spectrometric determination of copper in water samples

    OpenAIRE

    Lemos,Valfredo A; Santos, Juracir S.; Baliza,Patrícia X.

    2006-01-01

    A new preconcentration method using cloud point approach is proposed for copper determination. The reagent 2-[2´-(6-methyl-benzothiazolylazo)]-4-bromophenol (Me-BTABr) was used as a complexing agent and Triton X-114 was added as a surfactant. After phase separation, dilution of the surfactant-rich phase with acidified methanol was performed, and the copper content was measured by flame atomic absorption spectrometry. The proposed procedure allowed the determination of copper with detect...

  14. Mass spectrometric techniques for label-free high-throughput screening in drug discovery.

    Science.gov (United States)

    Roddy, Thomas P; Horvath, Christopher R; Stout, Steven J; Kenney, Kristin L; Ho, Pei-I; Zhang, Ji-Hu; Vickers, Chad; Kaushik, Virendar; Hubbard, Brian; Wang, Y Karen

    2007-11-01

    High-throughput screening (HTS) is an important tool for finding active compounds to initiate medicinal chemistry programs in pharmaceutical discovery research. Traditional HTS methods rely on fluorescent or radiolabeled reagents and/or coupling assays to permit quantitation of enzymatic target inhibition or activation. Mass spectrometry-based high-throughput screening (MS-HTS) is an alternative that is not susceptible to the limitations imposed by labeling and coupling enzymes. MS-HTS offers a selective and sensitive analytical method for unlabeled substrates and products. Furthermore, method development times are reduced without the need to incorporate labels or coupling assays. MS-HTS also permits screening of targets that are difficult or impossible to screen by other techniques. For example, enzymes that are challenging to purify can lead to the nonspecific detection of structurally similar components of the impure enzyme or matrix of membraneous enzymes. The high selectivity of tandem mass spectrometry (MS/MS) enables these screens to proceed with low levels of background noise to sensitively discover interesting hits even with relatively weak activity. In this article, we describe three techniques that we have adapted for large-scale (approximately 175,000 sample) compound library screening, including four-way parallel multiplexed electrospray liquid chromatography tandem mass spectrometry (MUX-LC/MS/MS), four-way parallel staggered gradient liquid chromatography tandem mass spectrometry (LC/MS/MS), and eight-way staggered flow injection MS/MS following 384-well plate solid-phase extraction (SPE). These methods are capable of analyzing a 384-well plate in 37 min, with typical analysis times of less than 2 h. The quality of the MS-HTS approach is demonstrated herein with screening data from two large-scale screens.

  15. Simultaneous Laser Thermal Lens Spectrometric Determination of Trace Platinum and Palladium in an Aqueous Solution

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Xiao-Ling(张小玲); YAN,Hong-Tao(阎宏涛)

    2002-01-01

    A selective and sensitive method for determination of platinum and palladium(Ⅱ) in an aqueous solntion simultaneously by laser thermal lens spectrometry, based on the complex reaction of 2- (3,5-dichloropyridylazo)-5- dimethylaminoamiline (3,5-diCl-PADMA) with platinum and palladium, has been developed. It is shown that the palladium complex can be formed at room temperature, while the platinum complex can be only formed after being heated in a boiling water bath. By using this difference of reaction temperature and the characteristic of the complexes mentioned above, the method for simultaneous determination of platinum and palladium was established in an aqueous solution without a pre-separation. The results show that the dynamic linear ranges of determination for platinum and pallladium are 0.005-0.04 μg/mL and 0.005-0.25 μg/mL respectively, and that the detection limits are both 0.002 μg/mL. The method has been applied to the determination of platinum and palladium simultaneously in alloy and catalyst samples with satisfactory results.

  16. Simultaneous Laser Thermal Lens Spectrometric Determination of Trace Platinum and Palladium in an Aquesous Solution

    Institute of Scientific and Technical Information of China (English)

    张小玲; 阎宏涛

    2002-01-01

    A selective and sensitive method for determination of platinum and palladium(Ⅱ)in an aqueous solution simultaneously by laser thermal lens spectrometry,based on the complex reaction of 2-(3,5-dichloropyridylazo)-5-dimethylaminoamiline(3,5-diCl-PADMA) with platinum and palladium,has been developed.It is shown that the palladium complex can be fromed at room temperature, while the platinum complex can be only formed after being heated in a boiling water bath.By using this difference of reaction temperature and the characteristic of the complexes mentioned above,the method for simultaneous determination of platinum and palladium was established in an aqueous solution without a pre-separation.The results show that the dynamic linear ranges of determination for platinum and palladium are 0.005-0.04μg/mL and 0.005-0.25μg/mL respectively,and that the detection limits are both 0.002/μg/mL.The method has been applied to the determination of platinum and palladium simultaneously in alloy and catalyst samples with satisfactory results.

  17. Mass spectrometric base composition profiling: Implications for forensic mtDNA databasing☆

    Science.gov (United States)

    Eduardoff, Mayra; Huber, Gabriela; Bayer, Birgit; Schmid, Dagmar; Anslinger, Katja; Göbel, Tanja; Zimmermann, Bettina; Schneider, Peter M.; Röck, Alexander W.; Parson, Walther

    2013-01-01

    In forensic genetics mitochondrial DNA (mtDNA) is usually analyzed by direct Sanger-type sequencing (STS). This method is known to be laborious and sometimes prone to human error. Alternative methods have been proposed that lead to faster results. Among these are methods that involve mass-spectrometry resulting in base composition profiles that are, by definition, less informative than the full nucleotide sequence. Here, we applied a highly automated electrospray ionization mass spectrometry (ESI-MS) system (PLEX-ID) to an mtDNA population study to compare its performance with respect to throughput and concordance to STS. We found that the loss of information power was relatively low compared to the gain in speed and analytical standardization. The detection of point and length heteroplasmy turned out to be roughly comparable between the technologies with some individual differences related to the processes. We confirm that ESI-MS provides a valuable platform for analyzing mtDNA variation that can also be applied in the forensic context. PMID:24054029

  18. A High Throughput Ambient Mass Spectrometric Approach to Species Identification and Classification from Chemical Fingerprint Signatures

    Science.gov (United States)

    Musah, Rabi A.; Espinoza, Edgard O.; Cody, Robert B.; Lesiak, Ashton D.; Christensen, Earl D.; Moore, Hannah E.; Maleknia, Simin; Drijfhout, Falko P.

    2015-07-01

    A high throughput method for species identification and classification through chemometric processing of direct analysis in real time (DART) mass spectrometry-derived fingerprint signatures has been developed. The method entails introduction of samples to the open air space between the DART ion source and the mass spectrometer inlet, with the entire observed mass spectral fingerprint subjected to unsupervised hierarchical clustering processing. A range of both polar and non-polar chemotypes are instantaneously detected. The result is identification and species level classification based on the entire DART-MS spectrum. Here, we illustrate how the method can be used to: (1) distinguish between endangered woods regulated by the Convention for the International Trade of Endangered Flora and Fauna (CITES) treaty; (2) assess the origin and by extension the properties of biodiesel feedstocks; (3) determine insect species from analysis of puparial casings; (4) distinguish between psychoactive plants products; and (5) differentiate between Eucalyptus species. An advantage of the hierarchical clustering approach to processing of the DART-MS derived fingerprint is that it shows both similarities and differences between species based on their chemotypes. Furthermore, full knowledge of the identities of the constituents contained within the small molecule profile of analyzed samples is not required.

  19. Photochemical vapor generation of lead for inductively coupled plasma mass spectrometric detection

    Science.gov (United States)

    Duan, Hualing; Zhang, Ningning; Gong, Zhenbin; Li, Weifeng; Hang, Wei

    2016-06-01

    Photochemical vapor generation (PCVG) of lead was successfully achieved with a simplified and convenient system, in which only low molecular weight organic acid and a high-efficiency photochemical reactor were needed. The reactor was used to generate lead volatile species when a solution of lead containing a small amount of low molecular weight organic acid was pumped through. Several factors, including the concentration of acetic acid, the concentration of hydrochloride acid, and the irradiation time of UV light were optimized. Under the optimal conditions, including the addition of 0.90% (v/v) acetic acid and 0.03% (v/v) hydrochloride acid, and irradiation time of 28 s, intense and repeatable signal of lead volatile species was successfully obtained and identified with inductively coupled plasma mass spectrometry (ICPMS). In addition, the effects from inorganic anions and transition metal ions, including Cl-, NO3-, SO42 -, Cu2 +, Fe3 +, Co2 + and Ni2 +, were investigated, which suggests that their suppression to the PCVG of lead was in the order of Cl- anions and Ni2 +, Co2 + < Fe3 + < Cu2 + for transition metal ions. Under optimized conditions, relative standard derivation (RSD) of 4.4% was achieved from replicate measurements (n = 5) of a standard solution of 0.1 μg L- 1 lead. And, the limit of quantitation (LOQ, 10σ) of 0.012 μg L- 1 lead was obtained using this method and the method blank could be easily controlled down to 0.023 μg L- 1. To validate applicability of this method, it was also employed for the determination of lead in tap water, rain water and lake water.

  20. Use of flow injection mass spectrometric fingerprinting and chemometrics for differentiation of three black cohosh species

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Huilian [Food Composition and Methods Development Laboratory, Beltsville Human Nutrition Research Center, Agricultural Research Service, U.S. Department of Agriculture, Beltsville, MD (United States); Key Laboratory of Modern Preparation of TCM, Jiangxi University of Traditional Chinese Medicine, Ministry of Education, Nanchang, Jiangxi Province (China); Sun, Jianghao [Food Composition and Methods Development Laboratory, Beltsville Human Nutrition Research Center, Agricultural Research Service, U.S. Department of Agriculture, Beltsville, MD (United States); McCoy, Joe-Ann [The North Carolina Arboretum Germplasm Repository, UNC Affiliate Campus, Asheville, NC (United States); Zhong, Haiyan [College of Food Science and Engineering, Central South University of Forestry and Technology, Changsha, Hunan Province (China); Fletcher, Edward J. [Strategic Sourcing, Inc., Banner Elk, NC 28604 (United States); Harnly, James, E-mail: harnly.james@ars.usda.gov [Food Composition and Methods Development Laboratory, Beltsville Human Nutrition Research Center, Agricultural Research Service, U.S. Department of Agriculture, Beltsville, MD (United States); Chen, Pei, E-mail: pei.chen@ars.usda.gov [Food Composition and Methods Development Laboratory, Beltsville Human Nutrition Research Center, Agricultural Research Service, U.S. Department of Agriculture, Beltsville, MD (United States)

    2015-03-01

    Flow injection mass spectrometry (FIMS) was used to provide chemical fingerprints of black cohosh (Actaea racemosa L.) in a manner of minutes by omitting the separation step. This method has proven to be a powerful tool for botanical authentication and in this study it was used to distinguish between three Actaea species prior to a more detailed chemical analysis using ultra high-performance liquid chromatography high-resolution mass spectrometry (UHPLC–HRMS). Black cohosh has become increasingly popular as a dietary supplement in the United States for the treatment of symptoms related to menopause. However, it has been known to be adulterated with the Asian Actaea dahurica (Turcz. ex Fisch. & C.A.Mey.) Franch. species (syn. Cimicifuga dahurica (Turcz.) Maxim). Existing methods for identification of black cohosh and differentiation of Actaea species are usually lengthy, laborious, and lack robustness, often based on the comparison of a few pre-selected components. Chemical fingerprints were obtained for 77 black cohosh samples and their related species using FIMS in the negative ion mode. The analysis time for each sample was less than 2 min. All data were processed using principal component analysis (PCA). FIMS fingerprints could readily differentiate all three species. Representative samples from each of the three species were further examined using UHPLC–MS to provide detailed profiles of the chemical differences between the three species and were compared to the PCA loadings. This study demonstrates a simple, fast, and easy analytical method that can be used to differentiate A. racemosa, Actaea podocarpa, and A. dahurica. - Highlights: • Flow injection mass spectrometry (FIMS) was used to provide chemical fingerprints of black cohosh (Actaea racemosa L.) in a manner of minutes by omitting the separation step. • FIMS can discriminate between A. dahurica, A. podocarpa, and A. racemosa. • FIMS is a valuable screening tool for authentication of botanicals.

  1. Mass spectrometric analysis of chemical warfare agents in support of a chemical terrorist event

    Energy Technology Data Exchange (ETDEWEB)

    Hancock, J.R.; D' Agostino, P.A.; Chenier, C.L. [Defence R and D Canada Suffield, Medicine Hat, AB (Canada)

    2003-07-01

    Chemical warfare (CW) agents are considered to be any chemicals which, through their chemical action on life processes can cause death, temporary incapacitation or permanent harm to humans or animals. In Canada, the probability of a CW terrorist attack is low despite the catastrophic consequences that would result from such an attack. The three levels of government would be responding to such an event. CW agent response training for all levels of government is offered at Defence R and D Canada-Suffield. Appropriate samples must be collected for analysis in a laboratory, as such an event would lead to a criminal investigation. Research into new methods for the identification of CW agents is being conducted by the analytical laboratory at Defence R and D Canada-Suffield. Gas chromatography and mass spectrometry (GC-MS) are being used extensively to separate and characterize CW agents in organic extracts. In the case of aqueous samples, another method might be more appropriate, since additional sample handling is required before GC-MS analysis can be performed. Minimal sample handling is required when using liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) for direct analysis of CW agents. The authors demonstrated the use of LC-ESI-MS for analyzing CW agents and their hydrolysis products in aqueous samples. For the analysis of nerve agents and phosphonic acids in soil, comparable or superior results to organic extraction and GC-MS were obtained for aqueous extractions followed by LC-ESI-MS. The combination of GC-MS and LC-ESI-MS for the analysis of mustard related compounds in soil extracts from a former mustard storage area showed that the two methods are complementary in this situation. 9 refs., 3 tabs., 5 figs.

  2. Determination of Metformin in Human Plasma by Liquid Chromatography-tandem Mass Spectrometric Assay

    Institute of Scientific and Technical Information of China (English)

    WANG Jian; WANG Ying-wu; GU Jing-kai; WU Yi; WANG Yan

    2005-01-01

    @@ Introduction Metformin (1,1-dimethylbiguanide) (Fig. 1) is an oral anti-hyperglycemic agent used in the treatment of non-insulin-dependent diabetes mellitus (type Ⅱ). Owing to its weight-decreasing and serum lipid-normalizing effects, it is especially recommended for obese patients[1,2] Various analytical methods have been described for the measurement of metformin in biological fluids, including gas chromatography(GC)[3-5], capillary electrophoresis (CE)[6] and HPLC[7~16]with UV detection[7-12,17] HPLC-Mass spectrometry (LC/APCIMS/MS ) offers an attractive alternative to HPLC[18].

  3. Gamma-spectrometric determination of the sup 8 sup 9 Sr isotope half-life

    CERN Document Server

    Popov, Y S; Markushin, M N; Kupriyanov, V N; Timofeev, G A

    2002-01-01

    Using the method of semiconductor [Ge(Li)-detector] gamma-spectroscopy by the results of measurements of 913 keV ( sup 8 sup 9 Sr) gamma-line intensity for 6000 h, using as internal reference the 661.7 keV ( sup 1 sup 3 sup 7 Cs) gamma-line, the value of sup 8 sup 9 Sr isotope half-life has been calculated, which proved to be 1208+-9 h or 50.34+-0.37 days. Error is provided for confidential probability P = 0.95

  4. Autoresonant-spectrometric determination of the residual gas composition in the ALPHA experiment apparatus.

    Science.gov (United States)

    Amole, C; Ashkezari, M D; Baquero-Ruiz, M; Bertsche, W; Butler, E; Capra, A; Cesar, C L; Chapman, S; Charlton, M; Eriksson, S; Fajans, J; Friesen, T; Fujiwara, M C; Gill, D R; Gutierrez, A; Hangst, J S; Hardy, W N; Hayden, M E; Isaac, C A; Jonsell, S; Kurchaninov, L; Little, A; Madsen, N; McKenna, J T K; Menary, S; Napoli, S C; Nolan, P; Olchanski, K; Olin, A; Povilus, A; Pusa, P; Rasmussen, C Ø; Robicheaux, F; Sarid, E; Silveira, D M; Stracka, S; So, C; Thompson, R I; Turner, M; van der Werf, D P; Wurtele, J S; Zhmoginov, A

    2013-06-01

    Knowledge of the residual gas composition in the ALPHA experiment apparatus is important in our studies of antihydrogen and nonneutral plasmas. A technique based on autoresonant ion extraction from an electrostatic potential well has been developed that enables the study of the vacuum in our trap. Computer simulations allow an interpretation of our measurements and provide the residual gas composition under operating conditions typical of those used in experiments to produce, trap, and study antihydrogen. The methods developed may also be applicable in a range of atomic and molecular trap experiments where Penning-Malmberg traps are used and where access is limited.

  5. Autoresonant-spectrometric determination of the residual gas composition in the ALPHA experiment apparatus

    Energy Technology Data Exchange (ETDEWEB)

    Amole, C.; Capra, A.; Menary, S. [Department of Physics and Astronomy, York University, Toronto, Ontario M3J 1P3 (Canada); Ashkezari, M. D.; Hayden, M. E. [Department of Physics, Simon Fraser University, Burnaby, British Columbia V5A 1S6 (Canada); Baquero-Ruiz, M.; Chapman, S.; Little, A.; Povilus, A.; So, C.; Turner, M. [Department of Physics, University of California, Berkeley, California 94720-7300 (United States); Bertsche, W. [Department of Physics, Swansea University, Swansea SA2 8PP (United Kingdom); School of Physics and Astronomy, University of Manchester, Manchester M13 9PL, United Kingdom and The Cockcroft Institute, Daresbury Laboratory, Warrington WA4 4AD (United Kingdom); Butler, E. [Physics Department, CERN, CH-1211 Geneva 23 (Switzerland); Cesar, C. L.; Silveira, D. M. [Instituto de Fisica, Universidade Federal do Rio de Janeiro, Rio de Janeiro 21941-972 (Brazil); Charlton, M.; Eriksson, S.; Isaac, C. A.; Madsen, N.; Napoli, S. C. [Department of Physics, Swansea University, Swansea SA2 8PP (United Kingdom); Collaboration: ALPHA Collaboration; and others

    2013-06-15

    Knowledge of the residual gas composition in the ALPHA experiment apparatus is important in our studies of antihydrogen and nonneutral plasmas. A technique based on autoresonant ion extraction from an electrostatic potential well has been developed that enables the study of the vacuum in our trap. Computer simulations allow an interpretation of our measurements and provide the residual gas composition under operating conditions typical of those used in experiments to produce, trap, and study antihydrogen. The methods developed may also be applicable in a range of atomic and molecular trap experiments where Penning-Malmberg traps are used and where access is limited.

  6. A Fourier Transform Infrared Spectrophotometry Method Used For Oseltamivir Determination in Pharmaceutical Formulations

    OpenAIRE

    Aboul-Enein, Y; BUNACIU, Andrei; Nita, Sultana; FLESCHIN, Serban; AYDOGMUS, Zeynep

    2012-01-01

    A Fourier transform infrared (FT-IR) spectrometric method was developed for the rapid, direct measurement of oseltamivir phosphate (OP) in pharmaceutical formulations. Conventional KBr-spectra were compared for best determination of the active substance in pharmaceutical preparations. The Beer-Lambert law and two chemometric approaches, partial least squares (PLS) and principal component regression (PCR+) methods, were used in data processing. Key words: FT-IR analysis, oseltamivir, ...

  7. DEFINING ELEMENTAL COMPOSITION OF VEGETABLE HYDROCOLLOIDS USING THE ELECTRON PROBE MICROANALYSIS METHOD

    OpenAIRE

    2014-01-01

    In production of soft capsules, natural and semi-synthetic vegetative analogues for pharmaceutical gelatin are used. This work is devoted to defining elemental composition of vegetative analogs for pharmaceutical gelatin using the electron probe microanalysis method. The electron probe microanalysis is one of the most popular methods of quantitative and semi-quantitative nondestructive elemental analysis. Spectrometric profiles are described for defining the composition of carboxymethylcellul...

  8. The effect of metal ions on Staphylococcus aureus revealed by biochemical and mass spectrometric analyses.

    Science.gov (United States)

    Chudobova, Dagmar; Dostalova, Simona; Ruttkay-Nedecky, Branislav; Guran, Roman; Rodrigo, Miguel Angel Merlos; Tmejova, Katerina; Krizkova, Sona; Zitka, Ondrej; Adam, Vojtech; Kizek, Rene

    2015-01-01

    In this study, we focused on the effect of heavy metal ions in resistant strains of gram-positive bacteria Staphylococcus aureus using biochemical methods and mass spectrometry. Five nitrate solutions of heavy metals (Ag(+), Cu(2+), Cd(2+), Zn(2+) and Pb(2+)) were used to create S. aureus resistant strains. Biochemical changes of resistant strains in comparison with the non-resistant control strain of S. aureus were observed by microbiological (measuring - growth curves and inhibition zones) and spectrophotometric methods (antioxidant activity and alaninaminotransferase, aspartateaminotransferase, alkaline phosphatase, γ-glutamyltransferase activities). Mass spectrometry was employed for the qualitative analysis of the samples (changes in S. aureus protein composition) and for the identification of the strains database MALDI Biotyper was employed. Alterations, in terms of biochemical properties and protein composition, were observed in resistant strains compared to non-resistant control strain. Our results describe the possible option for the analysis of S. aureus resistant strains and may thus serve as a support for monitoring of changes in genetic information caused by the forming of resistance to heavy metals.

  9. Doping control analysis of trimetazidine and characterization of major metabolites using mass spectrometric approaches.

    Science.gov (United States)

    Sigmund, Gerd; Koch, Anja; Orlovius, Anne-Katrin; Guddat, Sven; Thomas, Andreas; Schänzer, Wilhelm; Thevis, Mario

    2014-01-01

    Since January 2014, the anti-anginal drug trimetazidine [1-(2,3,4-trimethoxybenzyl)-piperazine] has been classified as prohibited substance by the World Anti-Doping Agency (WADA), necessitating specific and robust detection methods in sports drug testing laboratories. In the present study, the implementation of the intact therapeutic agent into two different initial testing procedures based on gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) is reported, along with the characterization of urinary metabolites by electrospray ionization-high resolution/high accuracy (tandem) mass spectrometry. For GC-MS analyses, urine samples were subjected to liquid-liquid extraction sample preparation, while LC-MS/MS analyses were conducted by established 'dilute-and-inject' approaches. Both screening methods were validated for trimetazidine concerning specificity, limits of detection (0.5-50 ng/mL), intra-day and inter-day imprecision (doping control samples were used to complement the LC-MS/MS-based assay, although intact trimetazidine was found at highest abundance of the relevant trimetazidine-related analytes in all tested sports drug testing samples. Retrospective data mining regarding doping control analyses conducted between 1999 and 2013 at the Cologne Doping Control Laboratory concerning trimetazidine revealed a considerable prevalence of the drug particularly in endurance and strength sports accounting for up to 39 findings per year.

  10. Chromatographic and mass spectrometric characterization of essential oils and extracts from Lippia (Verbenaceae) aromatic plants.

    Science.gov (United States)

    Stashenko, Elena E; Martínez, Jairo R; Cala, Mónica P; Durán, Diego C; Caballero, Deyanira

    2013-01-01

    Analytical methodologies based on GC and HPLC were developed for the separation and quantification of carnosic acid, ursolic acid, caffeic acid, p-coumaric acid, rosmarinic acid, apigenin, luteolin, quercetin, kaempferol, naringenin, and pinocembrin. These methods were used to characterize essential oils and extracts obtained by solvent (methanol) and by supercritical fluid (CO(2)) extraction from stems and leaves of Lippia (Verbenaceae family) aromatic plants (Lippia alba, Lippia origanoides, Lippia micromera, Lippia americana, Lippia graveolens, and Lippia citriodora). Supercritical CO(2) extraction isolated solely pinocembrin and narigenin from three L. origanoides chemotypes. Solvent extracts possessed a more varied composition that additionally included apigenin, quercetin, and luteolin. Solvent extraction afforded higher overall flavonoid yields from all species in comparison with supercritical CO(2) extraction. Pinocembrin was determined in L. origanoides extract at a concentration of 30 mg/g of plant material, which is more than ten times higher than the amount at which polyphenols are regularly found in aromatic plant extracts.

  11. Gamma-spectrometric determination of {sup 232}U in uranium-bearing materials

    Energy Technology Data Exchange (ETDEWEB)

    Zsigrai, Jozsef [European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), 76125 Karlsruhe, P.O. Box 2340 (Germany); Nguyen, Tam Cong [Centre for Energy Research of the Hungarian Academy of Sciences (EK), 1525 Budapest 114, P.O. Box 49 (Hungary); Berlizov, Andrey [European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), 76125 Karlsruhe, P.O. Box 2340 (Germany)

    2015-09-15

    The {sup 232}U content of various uranium-bearing items was measured using low-background gamma spectrometry. The method is independent of the measurement geometry, sample form and chemical composition. Since {sup 232}U is an artificially produced isotope, it carries information about previous irradiation of the material, which is relevant for nuclear forensics, nuclear safeguards and for nuclear reactor operations. A correlation between the {sup 232}U content and {sup 235}U enrichment of the investigated samples has been established, which is consistent with theoretical predictions. It is also shown how the correlation of the mass ratio {sup 232}U/{sup 235}U vs. {sup 235}U content can be used to distinguish materials contaminated with reprocessed uranium from materials made of reprocessed uranium.

  12. The importance of mass spectrometric dereplication in fungal secondary metabolite analysis

    DEFF Research Database (Denmark)

    Nielsen, Kristian Fog; Larsen, Thomas Ostenfeld

    2015-01-01

    in combination with chemical databases (e.g., AntiBase) to dereplicate known compounds. This has led to a continuous effort to improve chromatographic separation in conjunction with improvement in HRMS detection. Major improvements have also occurred with 2D chromatography, ion-mobility, MS/MS and MS3, stable...... isotope labeling feeding experiments, classic UV/Vis, and especially automated data-mining and metabolomics software approaches as the sheer amount of data generated is now the major challenge. This review will focus on the development and implementation of dereplication strategies and will highlight...... the importance of each stage of the process from sample preparation to chromatographic separation and finally toward both manual and more targeted methods for automated dereplication of fungal natural products using state-of-the art MS instrumentation....

  13. On the accuracy of gamma spectrometric isotope ratio measurements of uranium

    Energy Technology Data Exchange (ETDEWEB)

    Ramebäck, H., E-mail: henrik.ramebeck@foi.se [Swedish Defence Research Agency, FOI, CBRN Defence and Security, SE-901 82 Umeå (Sweden); Chalmers University of Technology, Department of Chemistry and Chemical Engineering, SE-412 96 Göteborg (Sweden); Lagerkvist, P.; Holmgren, S.; Jonsson, S.; Sandström, B.; Tovedal, A. [Swedish Defence Research Agency, FOI, CBRN Defence and Security, SE-901 82 Umeå (Sweden); Vesterlund, A. [Swedish Defence Research Agency, FOI, CBRN Defence and Security, SE-901 82 Umeå (Sweden); Chalmers University of Technology, Department of Chemistry and Chemical Engineering, SE-412 96 Göteborg (Sweden); Vidmar, T. [SCK-CEN, Belgian Nuclear Research Centre, Boeretang 200, 2400 Mol (Belgium); Kastlander, J. [Swedish Defence Research Agency, FOI, Defence and Security, Systems and Technology, SE-164 90 Stockholm (Sweden)

    2016-04-11

    The isotopic composition of uranium was measured using high resolution gamma spectrometry. Two acid solutions and two samples in the form of UO{sub 2} pellets were measured. The measurements were done in close geometries, i.e. directly on the endcap of the high purity germanium detector (HPGe). Applying no corrections for count losses due to true coincidence summing (TCS) resulted in up to about 40% deviation in the abundance of {sup 235}U from the results obtained with mass spectrometry. However, after correction for TCS, excellent agreement was achieved between the results obtained using two different measurement methods, or a certified value. Moreover, after corrections, the fitted relative response curves correlated excellently with simulated responses, for the different geometries, of the HPGe detector.

  14. Gamma-spectrometric determination of 232U in uranium-bearing materials

    CERN Document Server

    Zsigrai, Jozsef; Berlizov, Andriy

    2015-01-01

    The 232U content of various uranium-bearing items was measured using low-background gamma-spectrometry. The method is independent of the measurement geometry, sample form and chemical composition. Since 232U is an artificially produced isotope, it carries information about previous irradiation of the material, which is relevant for nuclear forensics, nuclear safeguards and for nuclear reactor operations. A correlation between the 232U content and 235U enrichment of the investigated samples has been established, which is consistent with theoretical predictions. It is also shown how the correlation of the mass ratio 232U/235U vs. 235U content can be used to distinguish materials contaminated with reprocessed uranium from materials made of reprocessed uranium.

  15. Fingerprinting Breast Cancer vs. Normal Mammary Cells by Mass Spectrometric Analysis of Volatiles

    Science.gov (United States)

    He, Jingjing; Sinues, Pablo Martinez-Lozano; Hollmén, Maija; Li, Xue; Detmar, Michael; Zenobi, Renato

    2014-06-01

    There is increasing interest in the development of noninvasive diagnostic methods for early cancer detection, to improve the survival rate and quality of life of cancer patients. Identification of volatile metabolic compounds may provide an approach for noninvasive early diagnosis of malignant diseases. Here we analyzed the volatile metabolic signature of human breast cancer cell lines versus normal human mammary cells. Volatile compounds in the headspace of conditioned culture medium were directly fingerprinted by secondary electrospray ionization-mass spectrometry. The mass spectra were subsequently treated statistically to identify discriminating features between normal vs. cancerous cell types. We were able to classify different samples by using feature selection followed by principal component analysis (PCA). Additionally, high-resolution mass spectrometry allowed us to propose their chemical structures for some of the most discriminating molecules. We conclude that cancerous cells can release a characteristic odor whose constituents may be used as disease markers.

  16. Sensitive and specific liquid chromatographic-tandem mass spectrometric assay for barnidipine in human plasma.

    Science.gov (United States)

    Pawula, M; Watson, D; Teramura, T; Watanabe, T; Higuchi, S; Cheng, K N

    1998-11-20

    A sensitive and specific LC-MS-MS assay has been developed and validated for barnidipine (1-benzyl-3-pyrrolidinyl)methyl-2,6-dimethyl-4(m-nitrophenyl)-1,4-dihydr opyridine-3,5-dicarboxylate). The assay involves a simple and rapid solid-phase extraction procedure. Sample analysis was on a Spherisorb S3ODS2 100 mmX2 mm I.D. column, with a Finnigan TSQ 7000 mass spectrometer, using an electrospray interface and selective reaction monitoring (SRM). The intra- and inter-day precision and accuracy, determined as the coefficient of variation and relative error, respectively, were 11.8% or less. The limit of quantitation was 0.03 ng/ml, and the calibration was linear between 0.03 and 3.0 ng/ml. The method has been used successfully for the measurement of over two thousand human plasma samples from pharmacokinetic clinical trials.

  17. Chromatographic isolation and mass spectrometric identification of a base-induced mebendazole fluorophor.

    Science.gov (United States)

    Baeyens, W; Abdel Fattah, F; De Moerloose, P

    1986-10-01

    Sodium hydroxide treatment of the benzoylbenzimidazole anthelmintics mebendazole and flubendazole produces yellow solutions that possess practically no fluorescence characteristics under various conditions. However, when spotting the alkaline solutions on filter paper and examining the spots under U.V., strong bluish-white fluorescence is obtained. When pouring liquid nitrogen over the spots, a very intense bluish-white fluorescence followed by a long-lasting greenish phosphorescence is observed. These luminescence phenomena allow visualization of 1 ng of mebendazole and of 5 ng of flubendazole per spot. A preparative separation by means of column liquid chromatography was worked out for the isolation of the fluorophor in case of mebendazole. Combined spectroscopic methods indicated the formation of a primary amine function in position 2 of the imidazole nucleus by hydrolytic cleavage of the -NH-CO-bond. A discussion on the mechanism of fluorescence is given.

  18. Mass spectrometric analysis of formalin-fixed paraffin-embedded tissue: unlocking the proteome within.

    Science.gov (United States)

    Hood, Brian L; Conrads, Thomas P; Veenstra, Timothy D

    2006-07-01

    The predominance of tissues stored worldwide in hospitals and clinical laboratories exist in formalin-fixed paraffin-embedded (FFPE) blocks that are generated by simple and well-established protocols. Although generation of FFPE tissues has facilitated their characterization by such techniques as histopathology, they have proven refractory to biomarker discovery investigations using state-of-the-art MS-based proteomic methodologies. Very recently new methods have been developed that enable proteins extracted from FFPE tissues to be analyzed by MS. This review will highlight and discuss those efforts that have led to this exciting recent progress. Although these developments are quite new, the ability to conduct MS-based proteomic analyses of FFPE tissues opens heretofore intractable clinical samples for discovery-based biomarker research.

  19. Inspection method for the identification of TBT-containing antifouling paints.

    Science.gov (United States)

    Senda, Tetsuya; Miyata, Osamu; Kihara, Takeshi; Yamada, Yasujiro

    2003-04-01

    In order to ensure the effectiveness of the international convention which will prohibit the use of organotin compounds in antifouling paints applied to ships, it is essential to establish an inspection system to determine the presence of the prohibited compounds in the paint. In the present study, a method for the identification of organotin containing antifouling paints using a two-stage analysis process is investigated. Firstly, X-ray fluorescence analysis (XRF) is utilized, which could be used at the place of ship surveys or port state control. Using a portable XRF instrument customized for ship inspection, analysis is automatically executed and determines whether tin is present or not. If the presence of tin is confirmed by XRF, the sample is subsequently examined at an analytical laboratory using more rigorous analytical techniques, such as gas chromatograph mass spectrometry (GC-MS). A sampling device has been designed. It is a disc of approximately 10 mm diameter and has abrasive paper pasted to one of its flat surfaces. The device is pressed onto and then slid along a ship hull to lightly scrape off fragments of paint onto the abrasive paper. Preliminary field tests have revealed that sampling from a ship in dock yields successful collection of the paint for XRD analysis and that the resultant damage caused to the antifouling paint surface by the sampling technique was found to be negligible.

  20. High performance liquid chromatography--atomic fluorescence spectrometric determination of arsenic species in beer samples

    Energy Technology Data Exchange (ETDEWEB)

    Melo Coelho, N.M.; Parrilla, Carmen; Cervera, M.L.; Pastor, A.; Guardia, M. de la

    2003-04-10

    A method has been developed for the direct determination of As(III), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and As(V) in beers by hydride generation--atomic fluorescence spectrometry after separation of arsenic species by high performance liquid chromatography. Compounds were separated by anion-exchange chromatography with isocratic elution using KH{sub 2}PO{sub 4}/K{sub 2}HPO{sub 4} as mobile phase with elution times of 1.67, 2.08, 6.52 and 10.72 min for As(III), DMA, MMA and As(V), respectively. Parameters affecting the hydride generation of all arsenic species were studied and the best conditions were established as a reaction coil of 150 cm, for a sample injected volume of 100 {mu}l, a 4.0% (m/v) solution of sodium tetrahydroborate and 2.0 mol l{sup -1} hydrochloric acid with flow rates of 2.7 and 1.7 ml min{sup -1}, respectively and a flow rate of 500 ml min{sup -1} for the argon carrier gas. Under the best experimental conditions, the detection limit was found to be 0.12, 0.20, 0.27 and 0.39 {mu}g l{sup -1} for As(III), DMA, MMA and As(V), respectively. The relative standard deviation for eight independent determinations varied from 3.9 till 8.9% for species considered at a concentration level of 10.0 {mu}g l{sup -1}. Recovery and comparative studies evidenced that the method is suitable for the accurate determination of arsenic species in water and beer samples.

  1. Liquid Chromatography-Tandem Mass Spectrometric Assay for Determination of Stavudine in Human Plasma

    Directory of Open Access Journals (Sweden)

    Fengdan Jin

    2014-01-01

    Full Text Available A LC-MS/MS method for determination of stavudine in human plasma was established and validated, and it was applied to the pharmaceutical formulations bioequivalence study. 0.5 mL plasma sample was extracted by liquid-liquid extraction. Stavudine was detected by a LC-MS/MS system. The pharmacokinetic parameters of stavudine in different formulations were calculated by noncompartment model statistics. The method was linear over the concentration ranges 5.00–1000 ng/mL in plasma. The intra- and interassay relative standard deviation (RSD was <10%. The average accuracies for the assay at three concentrations (5.00, 80.0, and 900 ng/mL were from 100.2% to 102.5%. Pharmacokinetic parameters of stavudine reference formulation were obtained as follows: Tmax was 0.6±0.2 h, Cmax was 480.7±150.9 g/L, t1/2 was 1.7±0.4 h, and AUC0-t was 872.8±227.8 g·h/L, and pharmacokinetic parameters of stavudine test formulation were obtained as follows: Tmax was 0.5±0.2 h, Cmax was 537.5±178.5 g/L, t1/2 was 1.7±0.3 h, and AUC0-t was (914.1±284.5 g·h/L. Calculated with AUC0-t, the bioavailability of two formulations was 105.0%.

  2. Flavonoids as matrices for MALDI-TOF mass spectrometric analysis of transition metal complexes

    Science.gov (United States)

    Petkovic, Marijana; Petrovic, Biljana; Savic, Jasmina; Bugarcic, Zivadin D.; Dimitric-Markovic, Jasmina; Momic, Tatjana; Vasic, Vesna

    2010-02-01

    Matrix-assisted laser desorption and ionization time-of-flight mass spectrometry (MALDI-TOF MS) is a suitable method for the analysis of inorganic and organic compounds and biomolecules. This makes MALDI-TOF MS convenient for monitoring the interaction of metallo-drugs with biomolecules. Results presented in this manuscript demonstrate that flavonoids such as apigenin, kaempferol and luteolin are suitable for MALDI-TOF MS analysis of Pt(II), Pd(II), Pt(IV) and Ru(III) complexes, giving different signal-to-noise ratios of the analyte peak. The MALDI-TOF mass spectra of inorganic complexes acquired with these flavonoid matrices are easy to interpret and have some advantages over the application of other commonly used matrices: a low number of matrix peaks are detectable and the coordinative metal-ligand bond is, in most cases, preserved. On the other hand, flavonoids do not act as typical matrices, as their excess is not required for the acquisition of MALDI-TOF mass spectra of inorganic complexes.

  3. Targeted and untargeted mass spectrometric approaches in discrimination between Myrtus communis cultivars from Sardinia region.

    Science.gov (United States)

    Sarais, G; D'Urso, G; Lai, C; Pirisi, F M; Pizza, C; Montoro, P

    2016-09-01

    In the present study, the discrimination of phytochemical content of Myrtus communis berries from different geographical origin and cultivars was explored by Liquid Chromatography-Electrospray Ionization-Fourier Transform-Mass Spectrometry (LC-ESI-FT-MS) metabolic profiling and quantitative analysis. Experiments were carried on myrtle plants grown in an experimental area of Sardinia region, obtained by the germination of seeds taken from berries collected in each part of the region. A preliminary untargeted approach on fruit's extracts was realized by collecting LC-ESI-FT-(Orbitrap)-MS data obtained by operating in negative ion mode and performing principal component analysis with the result of differentiation of samples. In a second step, targeted analysis with a reduced number of variables was realized. A data matrix was obtained by the data fusion of positive and negative ionization LC-ESI-MS results, by using as variables the peak areas of each known compounds. By the observation of principal component analysis, results found that anthocyanins, and mainly derivatives of cyanidin, are the principal marker compounds responsive for the discrimination of samples based on the geographical origin of the seeds. Based on this finding, finally, an LC-diode array detector method was developed, validated and applied for the quantitative analysis of berries' extracts based on 11 commercial standard compounds corresponding to the identified markers. Copyright © 2016 John Wiley & Sons, Ltd.

  4. Tandem mass spectrometric analysis of a complex triterpene saponin mixture of Chenopodium quinoa.

    Science.gov (United States)

    Madl, Tobias; Sterk, Heinz; Mittelbach, Martin; Rechberger, Gerald N

    2006-06-01

    A nano-HPLC electrospray ionization multi-stage tandem mass spectrometry (nLC-ESI-MS/MS) approach was applied to a complex crude triterpene saponin extract of Chenopodium quinoa seed coats. In ESI-MS/MS spectra of triterpene saponins, characteristic fragmentation reactions are observed and allow the determination of aglycones, saccharide sequences, compositions, and branching. Fragmentation of aglycones provided further structural information. The chemical complexity of the mixture was resolved by a complete profiling. Eighty-seven triterpene saponins comprising 19 reported and 68 novel components were identified and studied by MS. In addition to four reported, five novel triterpene aglycones were detected and characterized according to their fragmentation reactions in ESI-MS/MS and electron ionization mass spectrometry (EI-MS). As a novelty fragmentation pathways were proposed and analyzed based upon quantum chemical calculations using a hybrid Hartree-Fock density functional method. Accuracy of the assignment procedure was proven by isolation and structure determination of a novel compound. As the relative distribution and composition of saponins varies between different cultivars and soils, the presented strategy allows a rapid and complete analysis of Chenopodium quinoa saponin distribution and composition, and is particularly suitable for quality control and screening of extracts designated for pharmaceutical, agricultural, and industrial applications.

  5. Evaluation of HPGe spectrometric devices in monitoring the level of radioactive contamination in metallurgical industry

    Science.gov (United States)

    Petrucci, A.; Arnold, D.; Burda, O.; De Felice, P.; Garcia-Toraño, E.; Mejuto, M.; Peyres, V.; Šolc, J.; Vodenik, B.

    2015-10-01

    This paper presents the results of the tests of High Purity Germanium (HPGe) based gamma spectrometers employed for radioactivity control carried out on a daily basis in steel factories. This new application of this type of detector is part of the Joint Research Project (JRP) MetroMETAL supported by the European Metrology Research Programme (EMRP). The final purpose of the project was the improvement and standardisation of the measurement methods and systems for the control of radioactivity of recycled metal scraps at the beginning of the working process and for the certification of the absence of any radioactive contamination above the clearance levels (IAEA-TECDOC-8S5) in final steel products, Clearance levels for radionuclides in solid materials: application of exemption principles). Two prototypes based on HPGe detectors were designed and assembled to suit the needs of steel mills which had been examined previously. The evaluation of the two prototypes, carried out at three steel factories with standard sources of 60Co, 137Cs, 192Ir, 226Ra and 241Am in three different matrices (slag, fume dust and cast steel) and with samples provided on-site by the factories, was successful. The measurements proved the superiority of the prototypes over the scintillation detectors now commonly used regarding energy resolution and multi-nuclide identification capability. The detection limits were assessed and are presented as well.

  6. The importance of mass spectrometric dereplication in fungal secondary metabolite analysis

    Directory of Open Access Journals (Sweden)

    Kristian Fog Nielsen

    2015-02-01

    Full Text Available Having entered the Genomic Era, it is now evident that the biosynthetic potential of filamentous fungi is much larger than was thought even a decade ago. Fungi harbor many cryptic gene clusters encoding for the biosynthesis of polyketides, non-ribosomal peptides, and terpenoids – which can all undergo extensive modifications by tailoring enzymes – thus potentially providing a large array of products from a single pathway. Elucidating the full chemical profile of a fungal species is a challenging exercise, even with elemental composition provided by high-resolution mass spectrometry (HRMS used in combination with chemical databases (e.g. Antibase to dereplicate known compounds. This has led to a continuous effort to improve chromatographic separation in conjunction with improvement in HRMS detection. Major improvements have also occurred with 2D chromatography, ion-mobility, MS/MS and MS3, stable isotope labeling feeding experiments, classic UV/Vis, and especially automated data-mining and metabolomics software approaches as the sheer amount of data generated is now the major challenge. This review will focus on the development and implementation of dereplication strategies and will highlight the importance of each stage of the process from sample preparation to chromatographic separation and finally towards both manual and more targeted methods for automated dereplication of fungal natural products using state-of-the art MS instrumentation.

  7. [Spectrometric determination of trace elements in anticancer new medicine Fagopyrum dibotrys].

    Science.gov (United States)

    Wang, Ji-Yong; Wang, Yuan-Zhong; Zeng, Yan; Li, Jin-Tong

    2011-01-01

    The golden buckwheat Fagopyrum dibotrys produced in Yunnan has a unique anti-cancer effects. It is a main raw material of "Wei Mai ning" capsules which is the national second-class anti-cancer drug. The present paper used (5 : 1) mixed acid as digestive juice to process the sample, and determine the twelve elements including K, Ca, Cu, Na, Mg, Mn, Fe, Zn, Pb, Cr, Cd and Co in the Fagopyrum dibotrys by inductively coupled plasma atomic emission spectrometry(ICP-AES). The detection limits of this method were 0.017-0.084 microg x mL(-1), the RSDs (n = 8) were all 0.09%-1.87%, and the addition standard recoveries(ASR) (n = 8) were 98.2%-107.4% for all elements. The research results showed that there is rich K(1 477.3 microg x g(-1)) in the Fagopyrum dibotrys, there are not harmful elements Cd and Pb, and this result is mainly related to the geochemistry background where the sample lived. The contents of seven remaining kinds of elements ranked as Na (826.1) > Ca (765.2 > Mg (493.4) > Zn (112.7) > Fe (56.5) > Cu (11.4) > Mn (4.49 microg x g(-1)). This result provides some theoretical basis for the study of internal relations between trace elements in Fagopyrum dibotrys and efficacy. It' s also useful for better development and utilization of the resource.

  8. Mass spectrometric studies of lithium-containing oxides at high temperature

    Science.gov (United States)

    Ikeda, Yasushi; Tamaki, Masayoshi; Matsumoto, Genichi; Amioka, Kenji; Mizuno, Tomoyasu

    The sublimation and vaporization of various lithium containing oxides have been studied by high temperature mass spectrometry. The installed Knudsen cell apparatus gave some useful information about the vapor species, appearance potentials, partial pressures and heats of reactions involved. The investigated oxides are Li 2O, Li 2O-Al 2O 3, Li 2O-MoO 2 and Li 2O-SiO 2 systems. This paper mainly presents the most recent data for the Li 2O-SiO 2 system. A relationship for the decomposition reaction of ortho-Li 4SiO 4 was deduced. The heat of the reaction was determined by the third law method. The activity of the Li 2O component in the double oxides was estimated from the partial pressures of the vapor species. γ-LiAlO 2 and meta-Li 2SiO 3 showed fairly low activities in comparison with Li 2O oxide. The activity coefficients decreased with the Li 2O mole fraction in the lithium compounds. The heats of formation and atomization of LiO and Li 2O gaseous species were determined.

  9. Ultrahigh resolution mass spectrometric characterization of organic aerosol from European and Chinese cities

    Science.gov (United States)

    Wang, Kai; Huang, Ru-Jin; Hoffmann, Thorsten

    2016-04-01

    Organic aerosol constitutes a substantial fraction (20-90%) of submicrometer aerosol mass, playing an important role in air quality and human health. Over the past few years, ultra-high resolution mass spectrometry (UHRMS) has been applied to elucidate the chemical composition of ambient aerosols. However, most of the UHRMS studies used direct infusion without prior separation by liquid chromatography, which may cause the loss of individual compound information and interference problems. In the present study, urban ambient aerosol with particle diameter Beijing, China, respectively. Two pretreatment procedures were applied to extract the organic compounds from the filter samples: One method uses a mixture of acetonitrile and water, the other uses pure water and prepared for the extraction of humic-like substances. The extracts were analyzed by ultra-high-performance liquid chromatography coupled with an Orbitrap mass spectrometer in both negative and the positive modes. The effects of pretreatment procedures on the characterization of organic aerosol and the city-wise difference in chemical composition of organic aerosol will be discussed in detail.

  10. Evaluation of HPGe spectrometric devices in monitoring the level of radioactive contamination in metallurgical industry

    Energy Technology Data Exchange (ETDEWEB)

    Petrucci, A., E-mail: andrea.petrucci@enea.it [ENEA – Istituto Nazionale di Metrologia delle Radiazione Ionizzanti, Rome (Italy); Arnold, D.; Burda, O. [PTB – Physikalisch-Technische Bundesanstalt, Bundesallee 100, 38116 Braunschweig (Germany); De Felice, P. [ENEA – Istituto Nazionale di Metrologia delle Radiazione Ionizzanti, Rome (Italy); Garcia-Toraño, E.; Mejuto, M.; Peyres, V. [CIEMAT – Laboratorio de Metrologia de Radiaciones Ionizantes, Avda. Complutense 40, 28040 Madrid (Spain); Šolc, J. [CMI – Czech Metrology Institute, Radiova 1a, 102 00 Praha 10 (Czech Republic); Vodenik, B. [IJS – Laboratory for Radioactivity Measurements, Institute Jožef Stefan, Jamova 39, 1000 Ljubljana Slovenia (Slovenia)

    2015-10-11

    This paper presents the results of the tests of High Purity Germanium (HPGe) based gamma spectrometers employed for radioactivity control carried out on a daily basis in steel factories. This new application of this type of detector is part of the Joint Research Project (JRP) MetroMETAL supported by the European Metrology Research Programme (EMRP). The final purpose of the project was the improvement and standardisation of the measurement methods and systems for the control of radioactivity of recycled metal scraps at the beginning of the working process and for the certification of the absence of any radioactive contamination above the clearance levels (IAEA-TECDOC-8S5) in final steel products, Clearance levels for radionuclides in solid materials: application of exemption principles). Two prototypes based on HPGe detectors were designed and assembled to suit the needs of steel mills which had been examined previously. The evaluation of the two prototypes, carried out at three steel factories with standard sources of {sup 60}Co, {sup 137}Cs, {sup 192}Ir, {sup 226}Ra and {sup 241}Am in three different matrices (slag, fume dust and cast steel) and with samples provided on-site by the factories, was successful. The measurements proved the superiority of the prototypes over the scintillation detectors now commonly used regarding energy resolution and multi-nuclide identification capability. The detection limits were assessed and are presented as well.

  11. Data set for mass spectrometric analysis of recombinant human serum albumin from various expression systems

    Directory of Open Access Journals (Sweden)

    Daryl G.S. Smith

    2015-09-01

    Full Text Available Human serum albumin (HSA is a versatile and important protein for the pharmaceutical industry (Fanali et al., Mol. Aspects Med. 33(3 (2012 209–290. Due to the potential transmission of pathogens from plasma sourced albumin, numerous expression systems have been developed to produce recombinant HSA (rHSA (Chen et al., Biochim. Biophys. Acta (BBA—Gen. Subj. 1830(12 (2013 5515–5525; Kobayashi, Biologicals 34(1 (2006 55–59. Based on our previous study showing increased glycation of rHSA expressed in Asian rice (Frahm et al., J. Phys. Chem. B 116(15 (2012 4661–4670, both supplier-to-supplier and lot-to-lot variability of rHSAs from a number of expression systems were evaluated using reversed phase liquid chromatography linked with MS and MS/MS analyses. The data are associated with the research article ‘Determination of Supplier-to-Supplier and Lot-to-Lot Variability in Glycation of Recombinant Human Serum Albumin Expressed in Oryza sativa’ where further analysis of rHSA samples with additional biophysical methods can be found (Frahm et al., PLoS ONE 10(9 (2014 e109893. We determined that all rHSA samples expressed in rice showed elevated levels of arginine and lysine hexose glycation compared to rHSA expressed in yeast, suggesting that the extensive glycation of the recombinant proteins is a by-product of either the expression system or purification process and not a random occurrence.

  12. Diagnostic Accuracy of MALDI Mass Spectrometric Analysis of Unfractionated Serum in Lung Cancer

    Science.gov (United States)

    Yildiz, Pinar B.; Shyr, Yu; Rahman, Jamshedur S. M.; Wardwell, Noel R.; Zimmerman, Lisa J.; Shakhtour, Bashar; Gray, William H.; Chen, Shuo; Li, Ming; Roder, Heinrich; Liebler, Daniel C.; Bigbee, William L.; Siegfried, Jill M.; Weissfeld, Joel L.; Gonzalez, Adriana L.; Ninan, Mathew; Johnson, David H.; Carbone, David P.; Caprioli, Richard M.; Massion, Pierre P.

    2014-01-01

    Purpose There is a critical need for improvements in the noninvasive diagnosis of lung cancer. We hypothesized that matrix-assisted laser desorption ionization mass spectrometry (MALDI MS) analysis of the most abundant peptides in the serum may distinguish lung cancer cases from matched controls. Patients and Methods We used MALDI MS to analyze unfractionated serum from a total of 288 cases and matched controls split into training (n = 182) and test sets (n = 106). We used a training–testing paradigm with application of the model profile defined in a training set to a blinded test cohort. Results Reproducibility and lack of analytical bias was confirmed in quality-control studies. A serum proteomic signature of seven features in the training set reached an overall accuracy of 78%, a sensitivity of 67.4%, and a specificity of 88.9%. In the blinded test set, this signature reached an overall accuracy of 72.6 %, a sensitivity of 58%, and a specificity of 85.7%. The serum signature was associated with the diagnosis of lung cancer independently of gender, smoking status, smoking pack-years, and C-reactive protein levels. From this signature, we identified three discriminatory features as members of a cluster of truncated forms of serum amyloid A. Conclusions We found a serum proteomic profile that discriminates lung cancer from matched controls. Proteomic analysis of unfractionated serum may have a role in the noninvasive diagnosis of lung cancer and will require methodological refinements and prospective validation to achieve clinical utility. PMID:17909350

  13. Mass spectrometric analysis of 40 S ribosomal proteins from Rat-1 fibroblasts.

    Science.gov (United States)

    Louie, D F; Resing, K A; Lewis, T S; Ahn, N G

    1996-11-01

    Although sequences of most mammalian ribosomal proteins are available, little is known about the post-translational processing of ribosomal proteins. To examine their post-translational modifications, 40 S subunit proteins purified from Rat-1 fibroblasts and their peptides were analyzed by liquid chromatography coupled with electrospray mass spectrometry. Of 41 proteins observed, 36 corresponded to the 32 rat 40 S ribosomal proteins with known sequences (S3, S5, S7, and S24 presented in two forms). The observed masses of S4, S6-S8, S13, S15a, S16, S17, S19, S27a, S29, and S30 matched those predicted. Sa, S3a, S5, S11, S15, S18, S20, S21, S24, S26-S28, and an S7 variant showed changes in mass that were consistent with N-terminal demethionylation and/or acetylation (S5 and S27 also appeared to be internally formylated and acetylated, respectively). S23 appeared to be internally hydroxylated or methylated. S2, S3, S9, S10, S12, S14, and S25 showed changes in mass inconsistent with known covalent modifications (+220, -75, +86, +56, -100, -117, and -103 Da, respectively), possibly representing novel post-translational modifications or allelic sequence variation. Five unidentified proteins (12,084, 13,706, 13,741, 13,884, and 34, 987 Da) were observed; for one, a sequence tag (PPGPPP), absent in any known ribosomal proteins, was determined, suggesting that it is a previously undescribed ribosome-associated protein. This study establishes a powerful method to rapidly analyze protein components of large biological complexes and their covalent modifications.

  14. Mass spectrometric screening and identification of acidic metabolites in fulvic acid fractions of contaminated groundwater.

    Science.gov (United States)

    Jobelius, Carsten; Frimmel, Fritz H; Zwiener, Christian

    2014-05-01

    The anaerobic microbial degradation of aromatic and heterocyclic compounds is a prevalent process in contaminated groundwater systems. The introduction of functional groups into the contaminant molecules often results in aromatic and heterocyclic and succinic acids. These metabolites can be used as indicators for prevailing degradation processes. Therefore, there is a strong interest in developing analytical methods for screening and identification of these metabolites. In this study, neutral loss scans (NLS) by liquid chromatography-electrospray ionization/tandem mass spectrometry with losses of CO2 (NL ∆m/z = 44) and C2H4(CO2)2 (NL ∆m/z = 116) were applied for the first time successfully to screen selectively for acidic and succinic metabolites of aromatic and heterocyclic contaminants in two fulvic acid fractions from a contaminated site and a downstream region of a tar oil-polluted groundwater. Identification of these preselected signals was performed by high-resolution mass spectrometry with a liquid chromatography-electrospray ionization quadrupole time-of-flight mass spectrometry instrument. High-resolution mass and mass fragmentation data were then compared with a list of known metabolites from a literature search or matched with chemical databases supported with in silico fragmentation. Based on authentic analytical standards, several compounds from NLS were identified (e.g., 4-hydroxy-3-methylbenzoic acid, benzylsuccinic acid, naphthyl-2-methylsuccinic acid, 2-carboxyindane, and 2-carboxybenzothiophene) and tentatively identified (e.g., benzofuranmethylsuccinic acid and dihydrocarboxybenzothiophene) as aromatic, phenolic, heterocyclic, and succinic acids. The acidic metabolites were found exclusively in the contaminated region of the aquifer which indicates active biodegradation processes and no relevant occurrence of acidic metabolites in the downstream region.

  15. Vacuum-Ultraviolet Photoionization and Mass Spectrometric Characterization of Lignin Monomers Coniferyl and Sinapyl Alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Lynelle K.; Zhou, Jia; Kostko, Oleg; Golan, Amir; Leone, Stephen R.; Ahmed, Musahid

    2011-02-09

    The fragmentation mechanisms of monolignols under various energetic processes are studied with jet-cooled thermal desorption molecular beam (TDMB) mass spectrometry (MS), 25 keV Bi3+ secondary ion MS (SIMS), synchrotron vacuum-ultraviolet secondary neutral MS (VUV-SNMS) and theoretical methods. Experimental and calculated appearance energies of fragments observed in TDMB MS indicate that the coniferyl alcohol photoionization mass spectra contain the molecular parent and several dissociative photoionization products. Similar results obtained for sinapyl alcohol are also discussed briefly. Ionization energies of 7.60 eV ? 0.05 eV for coniferyl alcohol and<7.4 eV for both sinapyl and dihydrosinapyl alcohols are determined. The positive ion SIMS spectrum of coniferyl alcohol shares few characteristic peaks (m/z = 137 and 151) with the TDMB mass spectra, shows extensive fragmentation, and does not exhibit clear molecular parent signals. VUV-SNMS spectra, on the other hand, are dominated by the parent ion and main fragments also present in the TDMB spectra. Molecular fragmentation in VUV-SNMS spectra can be reduced by increasing the extraction delay time. Some features resembling the SIMS spectra are also observed in the desorbed neutral products. The monolignol VUV-SNMS peaks shared with the TDMB mass spectra suggest that dissociative photoionization of ion-sputtered neutral molecules predominate in the VUV-SNMS mass spectra, despite the extra internal energy imparted in the initial ion impact. The potential applications of these results to imaging mass spectrometry of bio-molecules are discussed.

  16. Characterization of Peptide Polymer Interactions in Poly(alkylcyanoacrylate) Nanoparticles: A Mass Spectrometric Approach.

    Science.gov (United States)

    Kafka, Alexandra P; Kleffmann, Torsten; Rades, Thomas; McDowell, Arlene

    2010-07-01

    Drug/polymer interactions occur during in situ polymerization of poly(alkylcyanoacrylate) (PACA) formulations. We have used MALDI ionization coupled tandem time-of-flight (TOF) mass spectrometry as an accurate method to characterize covalent peptide/polymer interactions of PACA nanoparticles with the bioactives D-Lys6-GnRH, insulin, [Asn1-Val5]-angiotensin II, and fragments of insulin-like growth factor 1 (IGF-1 (1-3)) and human adrenocorticotropic hormone (h-ACTH, (18-39)) at the molecular level. Covalent interactions of peptide with alkylcyanoacrylate were identified for D-Lys6-GnRH, [Asn1-Val5]-angiotensin II and IGF-1 (1-3). D-Lys6-GnRH and [Asn1-Val5]-angiotensin II were modified at their histidine side chain within the peptide, whilst IGF-1 (1-3) was modified at the C-terminal glutamic acid residue. The more complex protein insulin was not modified despite the presence of 2 histidine residues. This might be explained by the engagement of histidine residues in the folding and sterical arrangement of insulin under polymerization conditions. As expected, h-ACTH (18-39) that does not contain histidine residues did not interfere in the polymerization process. Lowering the pH did not prevent the covalent association of PACA with D-Lys6-GnRH or IGF-1 (1-3). Conclusively, protein and peptide bioactives are potentially reactive towards alkylcyanoacrylate monomers via various mechanisms with limited interference of pH. Histidines and C-terminal glutamic acid residues have been identified as potential sites of interaction. The likelihood of their engagement in the polymerization process (initiators), however, seems dependent on their sterical availability. The reactivity of nucleophilic functional groups should always be considered and bioactives examined for their potential to covalently interfere with alkylcyanoacrylate monomers, especially when designing PACA delivery systems for protein and peptide biopharmaceuticals.

  17. Mass spectrometric characterization of a prolyl hydroxylase inhibitor GSK1278863, its bishydroxylated metabolite, and its implementation into routine doping controls.

    Science.gov (United States)

    Thevis, Mario; Milosovich, Susan; Licea-Perez, Hermes; Knecht, Dana; Cavalier, Tom; Schänzer, Wilhelm

    2016-08-01

    Drug candidates, which have the potential of enhancing athletic performance represent a risk of being misused in elite sport. Therefore, there is a need for early consideration by anti-doping authorities and implementation into sports drug testing programmes. The hypoxia-inducible factor (HIF) or prolyl hydroxylase inhibitor (PHI) GSK1278863 represents an advanced candidate of an emerging class of therapeutics that possess substantial potential for abuse in sport due to their capability to stimulate the biogenesis of erythrocytes and, consequently, the individual's oxygen transport capacity. A thorough characterization of such analytes by technologies predominantly used for doping control purposes and the subsequent implementation of the active drug and/or its main urinary metabolite(s) are vital for comprehensive, preventive, and efficient anti-doping work. In the present study, the HIF PHI drug candidate GSK1278863 (comprising a 6-hydroxypyrimidine-2,4-dione nucleus) and its bishydroxylated metabolite M2 (GSK2391220A) were studied regarding their mass spectrometric behaviour under electrospray ionization (ESI-MS/MS) conditions. Synthesized reference materials were used to elucidate dissociation pathways by means of quadrupole/time-of-flight high resolution/high accuracy tandem mass spectrometry, and their detection from spiked urine and elimination study urine samples under routine doping control conditions was established using liquid chromatography-electrospray ionization-tandem mass spectrometry with direct injection. Dissociation pathways to diagnostic product ions of GSK1278863 (e.g. m/z 291, 223, and 122) were proposed as substantiated by determined elemental compositions and MS(n) experiments as well as comparison to spectra of the bishydroxylated analogue M2. An analytical assay based on direct urine injection using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) was developed for the simultaneous determination of GSK1278863 in

  18. Automated on-line liquid–liquid extraction system for temporal mass spectrometric analysis of dynamic samples

    Energy Technology Data Exchange (ETDEWEB)

    Hsieh, Kai-Ta; Liu, Pei-Han [Department of Applied Chemistry, National Chiao Tung University, 1001 University Rd, Hsinchu, 300, Taiwan (China); Urban, Pawel L. [Department of Applied Chemistry, National Chiao Tung University, 1001 University Rd, Hsinchu, 300, Taiwan (China); Institute of Molecular Science, National Chiao Tung University, 1001 University Rd, Hsinchu, 300, Taiwan (China)

    2015-09-24

    Most real samples cannot directly be infused to mass spectrometers because they could contaminate delicate parts of ion source and guides, or cause ion suppression. Conventional sample preparation procedures limit temporal resolution of analysis. We have developed an automated liquid–liquid extraction system that enables unsupervised repetitive treatment of dynamic samples and instantaneous analysis by mass spectrometry (MS). It incorporates inexpensive open-source microcontroller boards (Arduino and Netduino) to guide the extraction and analysis process. Duration of every extraction cycle is 17 min. The system enables monitoring of dynamic processes over many hours. The extracts are automatically transferred to the ion source incorporating a Venturi pump. Operation of the device has been characterized (repeatability, RSD = 15%, n = 20; concentration range for ibuprofen, 0.053–2.000 mM; LOD for ibuprofen, ∼0.005 mM; including extraction and detection). To exemplify its usefulness in real-world applications, we implemented this device in chemical profiling of pharmaceutical formulation dissolution process. Temporal dissolution profiles of commercial ibuprofen and acetaminophen tablets were recorded during 10 h. The extraction-MS datasets were fitted with exponential functions to characterize the rates of release of the main and auxiliary ingredients (e.g. ibuprofen, k = 0.43 ± 0.01 h{sup −1}). The electronic control unit of this system interacts with the operator via touch screen, internet, voice, and short text messages sent to the mobile phone, which is helpful when launching long-term (e.g. overnight) measurements. Due to these interactive features, the platform brings the concept of the Internet-of-Things (IoT) to the chemistry laboratory environment. - Highlights: • Mass spectrometric analysis normally requires sample preparation. • Liquid–liquid extraction can isolate analytes from complex matrices. • The proposed system automates

  19. MALDI-mass spectrometric imaging revealing hypoxia-driven lipids and proteins in a breast tumor model

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Jiang; Chughtai, Kamila; Purvine, Samuel O.; Bhujwalla, Zaver M.; Raman, Venu; Pasa-Tolic, Ljiljana; Heeren, Ronald M.; Glunde, Kristine

    2015-06-16

    Hypoxic areas are a common feature of rapidly growing malignant tumors and their metastases, and are typically spatially heterogeneous. Hypoxia has a strong impact on tumor cell biology and contributes to tumor progression in multiple ways. To date, only a few molecular key players in tumor hypoxia, such as for example hypoxia-inducible factor-1 (HIF-1), have been discovered. The distribution of biomolecules is frequently heterogeneous in the tumor volume, and may be driven by hypoxia and HIF-1α. Understanding the spatially heterogeneous hypoxic response of tumors is critical. Mass spectrometric imaging (MSI) provides a unique way of imaging biomolecular distributions in tissue sections with high spectral and spatial resolution. In this paper, breast tumor xenografts grown from MDA-MB-231-HRE-tdTomato cells, with a red fluorescent tdTomato protein construct under the control of a hypoxia response element (HRE)-containing promoter driven by HIF-1α, were used to detect the spatial distribution of hypoxic regions. We elucidated the 3D spatial relationship between hypoxic regions and the localization of small molecules, metabolites, lipids, and proteins by using principal component analysis – linear discriminant analysis (PCA-LDA) on 3D rendered MSI volume data from MDA-MB-231-HRE-tdTomato breast tumor xenografts. In this study we identified hypoxia-regulated proteins active in several distinct pathways such as glucose metabolism, regulation of actin cytoskeleton, protein folding, translation/ribosome, splicesome, the PI3K-Akt signaling pathway, hemoglobin chaperone, protein processing in endoplasmic reticulum, detoxification of reactive oxygen species, aurora B signaling/apoptotic execution phase, the RAS signaling pathway, the FAS signaling pathway/caspase cascade in apoptosis and telomere stress induced senescence. In parallel we also identified co-localization of hypoxic regions and various lipid species such as PC(16:0/18:1), PC(16:0/18:2), PC(18:0/18:1), PC

  20. The remote methods for radwaste and SNF control

    Science.gov (United States)

    Ivanov, O.; Stepanov, V.; Danilovich, A.; Potapov, V.

    2017-01-01

    With the examples of developments carried out in the Kurchatov Institute and by the world leaders in the field the presentation considers the devices and methods to obtain remotely information on the distribution of radioactivity in radwaste and SNF. It describes the different types of light portable gamma cameras. The application of scanning spectrometric systems is considers also. The methods of recording UV radiation for detection of alpha contamination with the luminescence of air are presented. We discuss the scope and tasks that can be solved using remote and non-destructive methods.

  1. Cloud point extraction and flame atomic absorption spectrometric determination of trace lead in freshwater fish%浊点萃取-火焰原子吸收光谱法测定淡水鱼中痕量铅

    Institute of Scientific and Technical Information of China (English)

    王秀峰; 李龙; 张春丽; 林朋; 崔书亚

    2012-01-01

    采用以双硫腙为络合剂、Triton X- 100为表面活性剂的新型浊点萃取体系富集淡水鱼中的痕量铅,并用火焰原子吸收光谱法对其进行测定.探讨了溶液pH、表面活性剂浓度、络合剂用量、平衡温度、平衡时间等对浊点萃取及测定灵敏度的影响,优化了实验条件.在最佳条件下测得铅的检出限为0.090μg/L,校准曲线相关系数为0.9999.该方法已用于淡水鱼中痕量铅的测定.%A new cloud point extraction-flame atomic absorption spectrometric method has been developed to determine trace lead. Dithizone was selected as the complex reagent and Triton X - 100 as the surfactant. Effects of pH, concentrations of surfactant and complex reagent, equilibrium temperature and time on the efficiency and sensitivity of cloud point extraction were investigated. Under optimal conditions, the calibration curve was linear over the concentration range of 0. 1 - 60μg/L with correlation coefficient of 0. 9999 and detection limit of 0. 090 μg/L. The present method was applied to the determination of trace lead in freshwater fish samples with satisfactory results.

  2. An ultra-high performance liquid chromatography-tandem mass spectrometric assay for quantifying 3-ketocholanoic acid: Application to the human liver microsomal CYP3A-dependent lithocholic acid 3-oxidation assay.

    Science.gov (United States)

    Bansal, Sumit; Chai, Swee Fen; Lau, Aik Jiang

    2016-06-15

    Lithocholic acid (LCA), a hepatotoxic and carcinogenic bile acid, is metabolized to 3-ketocholanoic acid (3-KCA) by cytochrome P450 3A (CYP3A). In the present study, the objectives were to develop and validate an ultra-high performance liquid chromatography-tandem mass spectrometric (UPLC-MS/MS) method to quantify 3-KCA and apply it to the human liver microsomal CYP3A-dependent LCA 3-oxidation assay. Chromatographic separation was achieved on a Waters ACQUITY™ UPLC C18 column (50×2.1mm, 1.7μm) with a gradient system consisting of 0.1% v/v formic acid in water (solvent A) and 0.1% v/v formic acid in acetonitrile (solvent B). The retention time was 3.73min for 3-KCA and 2.73min for cortisol (internal standard). Positive electrospray ionization with multiple reaction monitoring (MRM) mode was used to quantify 3-KCA (m/z 375.4→135.2) and cortisol (m/z 363.5→121.0). The limit of detection of 3-KCA was 10μM, the lower limit of quantification was 33.3μM, and the calibration curve was linear from 0.05-10μM with r(2)>0.99. Intra-day and inter-day accuracy and precision were Michaelis-Menten model with an apparent Km of 26±7μM and Vmax of 303±50pmol/min/mg protein. This novel UPLC-MS/MS method for quantifying 3-KCA offers a specific, sensitive, and fast approach to determine liver microsomal LCA 3-oxidation.

  3. A new ultrafast and high-throughput mass spectrometric approach for the therapeutic drug monitoring of the multi-targeted anti-folate pemetrexed in plasma from lung cancer patients

    NARCIS (Netherlands)

    R.J.W. Meesters (Roland); R. Cornelissen (Robin); R.J. van Klaveren (Rob); R. de Jonge (Robert); E. den Boer (Ethan); J. Lindemans (Jan); T.M. Luider (Theo)

    2010-01-01

    textabstractAn analytical assay has been developed and validated for ultrafast and high-throughput mass spectrometric determination of pemetrexed concentrations in plasma using matrix assisted laser desorption/ionization-triple quadrupole-tandem mass spectrometry. Patient plasma samples spiked with

  4. Automated sequential injection-microcolumn approach with on-line flame atomic absorption spectrometric detection for implementing metal fractionation schemes of homogeneous and non-homogeneous solid samples of environmental interest

    DEFF Research Database (Denmark)

    Chomchoei, Roongrat; Miró, Manuel; Hansen, Elo Harald

    2005-01-01

    spectrometric detection and used for the determination of Cu as a model analyte, the potentials of this novel hyphenated approach are demonstrated by the ability of handling up to 300 mg sample of a nonhomogeneous sewage amended soil (viz., CRM 483). The three steps of the endorsed Standards, Measurements...

  5. Development of a miniature dielectric barrier discharge–optical emission spectrometric system for bromide and bromate screening in environmental water samples

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Yong-Liang [Department of Chemistry, College of Sciences, Northeastern University, Box 332, Shenyang 110819 (China); Research Center for Analytical Sciences, College of Sciences, Northeastern University, Box 332, Shenyang 110819 (China); Cai, Yi [Research Center for Analytical Sciences, College of Sciences, Northeastern University, Box 332, Shenyang 110819 (China); Chen, Ming-Li, E-mail: chenml@mail.neu.edu.cn [Research Center for Analytical Sciences, College of Sciences, Northeastern University, Box 332, Shenyang 110819 (China); Wang, Jian-Hua, E-mail: jianhuajrz@mail.neu.edu.cn [Research Center for Analytical Sciences, College of Sciences, Northeastern University, Box 332, Shenyang 110819 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300071 (China)

    2014-01-27

    Graphical abstract: -- Highlights: •Dielectric barrier discharge (DBD) is for the first time used as a radiation source for the excitation of bromine and its emission. •A DBD–optical emission spectrometric (OES) system was developed for the detection of bromide and bromate. •The DBD–OES system has been demonstrated by screening trace bromide and bromate in a series of environmental water samples. -- Abstract: Dielectric barrier discharge (DBD) at atmospheric pressure provides an efficient radiation source for the excitation of bromine and it is used for the first time for optical emission spectrometric (OES) detection of bromide and bromate. A portable DBD–OES system is developed for screening potential pollution from bromide and bromate in environmental waters. Bromide is on-line oxidized to bromine for in-situ generation of volatile bromine. Meanwhile, a helium stream carries bromine into the DBD micro-plasma for its excitation at a discharging voltage of 3.7 kV and optical emission spectrometric detection with a QE65000 charge-coupled device (CCD) spectrometer in the near-infrared spectral region. Similarly, the quantification of bromate is performed by its pre-reduction into bromide and then oxidized to bromine. The spectral characteristics and configuration of the DBD micro-plasma excitation source in addition to the oxidation vapor generation of bromine have been thoroughly investigated. With a sampling volume of 1 mL, a linear range of 0.05–10.0 mg L{sup −1} is obtained with a detection limit of 0.014 mg L{sup −1} by measuring the emission at 827 nm. A precision of 2.3% is achieved at 3 mg L{sup −1} bromide. The system is validated by bromine detection in certified reference material of laver (GBW10023) at mg L{sup −1} level, giving rise to satisfactory agreement. In addition, it is further demonstrated by screening trace bromide and bromate as well as spiking recoveries in a series of environmental water samples.

  6. Monitoring of PAHs in air by collection on XAD-2 adsorbent then microwave-assisted thermal desorption coupled with headspace solid-phase microextraction and gas chromatography with mass spectrometric detection.

    Science.gov (United States)

    Wei, Ming-Chi; Chang, Wan-Ting; Jen, Jen-Fon

    2007-02-01

    Microwave-assisted thermal desorption (MAD) coupled to headspace solid-phase microextraction (HS-SPME) has been studied for in-situ, one-step, sample preparation for PAHs collected on XAD-2 adsorbent, before gas chromatography with mass spectrometric detection. The PAHs on XAD-2 were desorbed into the extraction solution, evaporated into the headspace by use of microwave irradiation, and absorbed directly on a solid-phase microextraction fiber in the headspace. After desorption from the SPME fiber in the hot GC injection port, PAHs were analyzed by GC-MS. Conditions affecting extraction efficiency, for example extraction solution, addition of salt, stirring speed, SPME fiber coating, sampling temperature, microwave power and irradiation time, and desorption conditions were investigated. Experimental results indicated that extraction of 275 mg XAD-2, containing 10-200 ng PAHs, with 10-mL ethylene glycol-1 mol L(-1) NaCl solution, 7:3, by irradiation with 120 W for 40 min (the same as the extraction time), and collection with a PDMS-DVB fiber at 35 degrees C, resulted in the best extraction efficiency. Recovery was more than 80% and RSD was less than 14%. Optimum desorption was achieved by heating at 290 degrees C for 5 min. Detection limits varied from 0.02 to 1.0 ng for different PAHs. A real sample was obtained by using XAD-2 to collect smoke from indoor burning of joss sticks. The amounts of PAHs measured varied from 0.795 to 2.53 ng. The method is a simple and rapid procedure for determination of PAHs on XAD-2 absorbent, and is free from toxic organic solvents.

  7. Mass Spectrometric Fragmentation of 1,8-Bis[4-substituted-(oxazolin-2-yl)] anthracenes: Ring-contraction Rearrangement of Oxazoline Ring under Electron-Impact Ionization Conditions

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The mass spectrometric fragmentation of 1,8-bis[4-substituted(oxazolin-2-yl)] anthracenes(AnBOXes) was investigated by using mass-analyzed ion kinetic energy spectrometry under electron-impact ionization conditions. All the compounds could undergo a ring contraction by the loss of an RCH=CH2 molecule to form 1-oxazirinyl-8-(oxazolin-2-yl) anthracene ions, which could further lose an R radical, followed by the loss of oxazoline. These ions could also eliminate an R radical and subsequently undergo ring-contraction rearrangements to lose a CHCH2O fragment and an epoxide molecule, respectively. The ions that are formed could further lose CHCH2O and CH2=CH fragments. Several ring-contraction rearrangements of the oxazoline ring were observed under electron-impact ionization conditions.

  8. Evaluation of capillary supercritical fluid chromatography with mass spectrometric detection for the analysis of a drug (mebeverine) in a dog plasma matrix.

    Science.gov (United States)

    Pinkston, J D; Venkatramani, C J; Tulich, L J; Bowling, D J; Wehmeyer, K R

    1993-12-22

    Supercritical fluid chromatography with mass spectrometric detection was evaluated as a technique for the analysis of drugs in biological fluids. Dog plasma was spiked with a model drug, mebeverine, and with a deuterium-labeled analog of mebeverine. The spiked plasma was prepared for analysis by solid-phase extraction on octadecylsilane cartridges. Mebeverine levels in the spiked dog plasma samples were determined by interpolation from a standard curve. Accuracy and precision of the analysis were determined within and between days. In general, accuracy was found to be 100 +/- 15% for plasma samples spiked with 6 to 60 ng mebeverine/ml. The relative standard deviation for replicate sample analysis over this concentration range was between 5 and 12.5%.

  9. Research of Spectrometric and Exploitation Characteristics of BGO-PMP-165 Scintiblock in Temperature Interval from +25 to -140$^{o}$C

    CERN Document Server

    Ainbund, M R; Gundorin, N A; Matveev, D V; Serov, D G

    2001-01-01

    Photomultipliers based on microchannel plates are used for fast systems which form time marks of physical setups as well as in special technical areas. It is not uncommon when they substitute traditional dynode system photomultipliers. The possibility of compatible work of the PMP-165 photomultiplier with BGO crystal which were cooled down to temperature necessary for appropriate functioning of a semiconductor Ge detector with taking into account of temperature dependencies of own PMP characteristics is investigated during experiment. Cooling down of the system from room temperature down to v140^{o}C during 8 hours is done. Lower limit of temperature which allows PMP to function properly is registered. Changes of spectrometric characteristics caused by temperature are studied.

  10. 《药物波谱解析》课程教学的改革与实践%Spectrometric Identification of Drug Molecules:Teaching Practice

    Institute of Scientific and Technical Information of China (English)

    李新

    2015-01-01

    Spectrometric Identification of Drug Molecules"is a very important course for pharmacy undergraduates. Many concepts in this course are profound and frustrating. Aiming to arouse the interest of students, we have explored a new way of lecturing.%药物波谱解析是药学专业中的重要课程之一,该课程有内容抽象,但实践和应用性强的特点。我们结合药学专业的学科特点,从教学方法和教学内容方面对该课程的教学改革进行了实践探索,为该课程教学工作提供参考。

  11. Gas chromatography/mass spectrometric analysis of methyl esters of N,N-dialkylaminoethane-2-sulfonic acids for verification of the Chemical Weapons Convention.

    Science.gov (United States)

    Pardasani, Deepak; Gupta, Arvinda K; Palit, Meehir; Shakya, Purushottam; Kanaujia, Pankaj K; Sekhar, K; Dubey, Devendra K

    2005-01-01

    This paper describes the synthesis and gas chromatography/electron ionization mass spectrometric (GC/EI-MS) analysis of methyl esters of N,N-dialkylaminoethane-2-sulfonic acids (DAESAs). These sulfonic acids are important environmental signatures of nerve agent VX and its toxic analogues, hence GC/EI-MS analysis of their methyl esters is of paramount importance for verification of the Chemical Weapons Convention. DAESAs were prepared by condensation of 2-bromoethane sulfonic acid with dialkylamines, and by condensation of dialkylaminoethyl chloride with sodium bisulfite. GC/EI-MS analysis of methyl esters of DAESAs yielded mass spectra; based on these spectra, generalized fragmentation routes are proposed that rationalize most of the characteristic ions.

  12. Performance analysis of gamma ray spectrometric parameters on digital signal and analog signal processing based MCA systems using NaI(Tl) detector

    Energy Technology Data Exchange (ETDEWEB)

    Kukreti, B.M., E-mail: bharatkuk@gmail.com [Atomic Minerals Directorate for Exploration and Research, Physics Laboratory, Department of Atomic Energy, Nongmynsong, AMD Complex, Shillong, Meghalaya 793019 (India); Sharma, G.K. [Atomic Minerals Directorate for Exploration and Research, Physics Laboratory, Department of Atomic Energy, Nongmynsong, AMD Complex, Shillong, Meghalaya 793019 (India)

    2012-05-15

    Accurate and speedy estimations of ppm range uranium and thorium in the geological and rock samples are most useful towards ongoing uranium investigations and identification of favorable radioactive zones in the exploration field areas. In this study with the existing 5 in. Multiplication-Sign 4 in. NaI(Tl) detector setup, prevailing background and time constraints, an enhanced geometrical setup has been worked out to improve the minimum detection limits for primordial radioelements K{sup 40}, U{sup 238} and Th{sup 232}. This geometrical setup has been integrated with the newly introduced, digital signal processing based MCA system for the routine spectrometric analysis of low concentration rock samples. Stability performance, during the long counting hours, for digital signal processing MCA system and its predecessor NIM bin based MCA system has been monitored, using the concept of statistical process control. Monitored results, over a time span of few months, have been quantified in terms of spectrometer's parameters such as Compton striping constants and Channel sensitivities, used for evaluating primordial radio element concentrations (K{sup 40}, U{sup 238} and Th{sup 232}) in geological samples. Results indicate stable dMCA performance, with a tendency of higher relative variance, about mean, particularly for Compton stripping constants. - Highlights: Black-Right-Pointing-Pointer Geometrical enhancement for ppm range primordial radio elemental determination. Black-Right-Pointing-Pointer Experimental constraints include detector setup, background and counting time. Black-Right-Pointing-Pointer Gamma spectrometric performance monitored on digital and analog MCA systems. Black-Right-Pointing-Pointer Study indicates higher variance of Compton stripping constants on digital MCA system.

  13. Development of high-spatial and high-mass resolution mass spectrometric imaging (MSI) and its application to the study of small metabolites and endogenous molecules of plants

    Energy Technology Data Exchange (ETDEWEB)

    Jun, Ji Hyun [Iowa State Univ., Ames, IA (United States)

    2012-01-01

    High-spatial and high-mass resolution laser desorption ionization (LDI) mass spectrometric (MS) imaging technology was developed for the attainment of MS images of higher quality containing more information on the relevant cellular and molecular biology in unprecedented depth. The distribution of plant metabolites is asymmetric throughout the cells and tissues, and therefore the increase in the spatial resolution was pursued to reveal the localization of plant metabolites at the cellular level by MS imaging. For achieving high-spatial resolution, the laser beam size was reduced by utilizing an optical fiber with small core diameter (25 μm) in a vacuum matrix-assisted laser desorption ionization-linear ion trap (vMALDI-LTQ) mass spectrometer. Matrix application was greatly improved using oscillating capillary nebulizer. As a result, single cell level spatial resolution of ~ 12 μm was achieved. MS imaging at this high spatial resolution was directly applied to a whole Arabidopsis flower and the substructures of an anther and single pollen grains at the stigma and anther were successfully visualized. MS imaging of high spatial resolution was also demonstrated to the secondary roots of Arabidopsis thaliana and a high degree of localization of detected metabolites was successfully unveiled. This was the first MS imaging on the root for molecular species. MS imaging with high mass resolution was also achieved by utilizing the LTQ-Orbitrap mass spectrometer for the direct identification of the surface metabolites on the Arabidopsis stem and root and differentiation of isobaric ions having the same nominal mass with no need of tandem mass spectrometry (MS/MS). MS imaging at high-spatial and high-mass resolution was also applied to cer1 mutant of the model system Arabidopsis thaliana to demonstrate its usefulness in biological studies and reveal associated metabolite changes in terms of spatial distribution and/or abundances compared to those of wild-type. The spatial

  14. 司法案例中芬那露的气相色谱-质谱分析%Analysis of Chlormethazanone by Gas Chromatography-Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    张莉英; 张春水; 郑珲

    2004-01-01

    Chlormethazanone was a medicine used for calming, A method the determination of chlormethazanone in human stomach and liver tissue by gas chromatographic-mass spectrometry was developed. This method had been successfully applied into judicial identification.

  15. Photoneutron spectrum measured with Bonner Spheres in Planetary method mode

    Energy Technology Data Exchange (ETDEWEB)

    Benites R, J. [Centro Estatal de Cancerologia de Nayarit, Servicio de Seguridad Radiologica, Calz. de la Cruz 118 Sur, 63000 Tepic, Nayarit (Mexico); Vega C, H. R. [Universidad Autonoma de Zacatecas, Unidad Academica de Estudios Nucleares, Apdo. Postal 336, 98000 Zacatecas (Mexico); Velazquez F, J., E-mail: jlbenitesr@prodigy.net.mx [Universidad Autonoma de Nayarit, Posgrado en Ciencias Biologico Agropecuarias, Carretera Tepic-Compostela Km 9, 63780 Jalisco-Nayarit (Mexico)

    2012-10-15

    We measured the spectrum of photoneutrons at 100 cm isocenter linear accelerator (Linac) Varian ix operating at 15 MV Bremsstrahlung mode. In this process was used a radiation field of 20 x 20 cm{sup 2} at a depth of 5 cm in a solid water phantom with dimensions of 30 x 30 x 15 cm{sup 3}. The measurement was performed with a system using it Bonner Spheres spectrometric method Planetary mode. As neutron detector of the spectrometer is used thermoluminescent dosimeters pairs of type 600 and 700. (Author)

  16. A Screening Method for the Identification of Glycosylated Flavonoids and Other Phenolic Compounds Using a Standard Analytical Approach for All Plant Materials

    OpenAIRE

    Lin, Long-Ze; Harnly, James M.

    2007-01-01

    A screening method was developed for the systematic identification of glycosylated flavonoids and other phenolic compounds in plant food materials based on an initial, standard analytical method. This approach applies the same analytical scheme (aqueous methanol extraction, reverse phase liquid chromatographic separation, and diode array and mass spectrometric detection) to every sample and standard. This standard approach allows the cross-comparison of compounds in samples, standards, and pl...

  17. Metabolism of cycloate in radish leaf: metabolite identification by packed capillary flow fast atom bombardment tandem mass spectrometry.

    Science.gov (United States)

    Onisko, B C; Barnes, J P; Staub, R E; Walker, F H; Kerlinger, N

    1994-10-01

    The metabolism of cycloate, a thiocarbamate herbicide, was investigated in mature radish leaf. Twelve new metabolites were identified by liquid chromatographic/mass spectrometric analysis using fast atom bombardment and packed capillary liquid chromatography columns. Full-scan and tandem mass spectrometric methods were employed. Application of the on-column focusing technique resulted in identifications with injections of as little as 15 ng of metabolite (20 ppb in radish). This injection technique allows the practical use of packed capillary liquid chromatography/mass spectrometry in sample-limited applications. Cycloate is oxidized to several ring-hydroxylated isomers that are subsequently glucosylated and esterified with malonic acid. Cycloate is also conjugated with glutathione. Metabolic hydrolysis of the glutathione conjugate formed a cysteine conjugate that is further metabolized by amidation with either malonic or acetic acid. Transamination of the cysteine conjugate gave a thiolactic acid derivative. Metabolites were also identified that were the result of both ring-hydroxylation and conjugation with glutathione. One of these, an N-acetylcysteine conjugate, is the first report of a mercapturic acid in plants. The structures of two of the new metabolites were confirmed by chemical synthesis.

  18. Determination of volatile organic compounds, catechins, caffeine and theanine in Jukro tea at three growth stages by chromatographic and spectrometric methods.

    Science.gov (United States)

    Jeon, Dong Bok; Hong, Young Shin; Lee, Ga Hyun; Park, Yu Min; Lee, Cheong Mi; Nho, Eun Yeong; Choi, Ji Yeon; Jamila, Nargis; Khan, Naeem; Kim, Kyong Su

    2017-03-15

    Tea contains characteristic volatile organic compounds, polyphenols, caffeine and catechins, and is therefore among the most widely consumed beverages all over the world. In this study, fresh Jukro tea leaves collected from Damyang-gun (Jeollanam-do) at 40, 60 and 90day growth stages, were semi-fermented. The volatile organic compounds (VOCs) were extracted by simultaneous distillation-solvent extraction (SDE) and analyzed by gas chromatography/mass spectrometry (GC/MS). Catechins, caffeine and theanine were analyzed by high performance liquid chromatography (HPLC). A total of 159 VOCs were identified in the analyzed Jukro tea leaves. Comparatively, the increase in the concentrations of VOCs was high in 60day leaves. The content of catechins increased along the three growth stages, whereas caffeine, compared to 90day leaves, was higher for 40 and 60day leaves. Based on the results, the 60day leaves were found to be the most suitable and useful for making semi-fermented Jukro tea.

  19. Enrichment and separation of mono- and multiply phosphorylated peptides using sequential elution from IMAC prior to mass spectrometric analysis

    DEFF Research Database (Denmark)

    Thingholm, Tine E; Jensen, Ole N; Larsen, Martin R

    2009-01-01

    Phospho-proteomics relies on methods for efficient purification and sequencing of phosphopeptides from highly complex biological systems using low amounts of starting material. Current methods for phosphopeptide enrichment, e.g., immobilized metal affinity chromatography and titanium dioxide...

  20. Analysis of Zolpidem in Postmortem Fluids and Tissues Using Ultra-Performance Liquid Chromatography-Mass Spectrometry

    Science.gov (United States)

    2014-02-01

    Peak plasma con- centrations occur at approximately 1.6 hr (5). When zolpidem is taken with food , blood concentrations are less. In blood, the...81-90. 2. U.S. Food and Drug Administration. FDA drug safety communication: FDA approves new label changes and dosing for zolpidem products and a...Accurate assignment of ethanol origin in postmor- tem urine: Liquid chromatographic-mass spectrometric determination of serotonin metabolites. J

  1. Quantification of ultra-trace amounts of copper by using off-line solid phase extraction-flame atomic absorption spectrometric determination through the octadecyl silica-bonded phase membrane (OSPM) C18 disks impregnated with 2,2'-[ethane-1,2-diylbis(thio)]dianiline.

    Science.gov (United States)

    Mohammadhosseini, Majid; Soliemani, Esmaeil

    2014-07-01

    This study reports a very selective, easy, and precise method for rapid separation of trace amounts of copper in aqueous samples using octadecyl silica-bonded phase membrane disks modified by 2,2'-[ethane-1,2-diylbis(thio)]dianiline (EDTD) combined with flame atomic absorption spectrometric determination. In addition, the synthesis and spectral characterization of EDTD have been described in detail. All the affecting experimental variables such as pH, amount of modifier, eluent type, sample and eluent flow rate, interfering ions, and disk capacity were also investigated. The target analyte (trace copper) was quantitatively retained at pH = 4 and eluted with 6.0 mL of 0.5 M HNO3 at flow rates of 40 and 10 mL min−1 for analyte passage and elution steps, respectively, through the disks modified with 17.0 mg of EDTD. The proposed method also allows an enrichment factor of about 500 and has a detection limit of 0.005 ng mL−1. The method has been successfully applied for isolation and determination of copper in different water samples, peppers, and standard alloys.

  2. Optimisation of spectrometric gamma-gamma probe configuration using very low radioactivity sources for lead and zinc grade determination in borehole logging

    CERN Document Server

    Asfahani, J

    1999-01-01

    The suitability of spectrometric backscattered gamma-gamma well logging measurements to predict lead and zinc metal equivalent content is demonstrated. A centralised tool employing a gamma-ray source of very low radioactivity (1.8 MBq) is used. The logging tool is tested using sup 1 sup 3 sup 3 Ba and sup 1 sup 3 sup 7 Cs sources with a 37 mm (diameter)x75 mm NaI (TI) scintillation detector. Five source-to-detector configurations were analysed for 18 geophysical models, 13 of which had a borehole diameter of 130 mm and the other 5 had a borehole diameter of 160 mm. Regression analysis on the laboratory logging data for each configuration in order to establish the calibration equation for a lead (Pb) and zinc metal equivalent (ZME) prediction is carried out. The optimum configuration for the logging probe using a sup 1 sup 3 sup 3 Ba source was determined to be 52 mm source-to-detector spacing. This configuration gives the best results for both Pb and ZME grade. The rms deviations for Pb and ZME were 0.33 and ...

  3. Favourable uranium-phosphate exploration trends guided by the application of statistical factor analysis technique on the aerial gamma spectrometric data in Syrian desert (Area-1), Syria

    Science.gov (United States)

    Asfahani, J.; Al-Hent, R.; Aissa, M.

    2016-02-01

    A scored lithological map including 10 radiometric units is established through applying factor analysis approach to aerial spectrometric data of Area-1, Syrian desert, which includes Ur, eU, eTh, K%, eU/eTh, eU/K%, and eTh/K%. A model of four rotated factors F1, F2, F3, and F4 is adapted for representing 234,829 data measured points in Area-1, where 86% of total data variance is interpreted. A geological scored pseudo-section derived from the lithological scored map is established and analyzed in order to show the possible stratigraphic and structural traps for uranium occurrences associated with phosphate deposits in the studied Area-1. These identified traps presented in this paper need detailed investigation and must be necessarily followed and checked by ground validations and subsurface well logging, in order to locate the anomalous uranium occurrences and explore with more confidence and certitude their characteristics as a function of depth.

  4. Favourable uranium–phosphate exploration trends guided by the application of statistical factor analysis technique on the aerial gamma spectrometric data in Syrian desert (Area-1), Syria

    Indian Academy of Sciences (India)

    J Asfahani; R Al-Hent; M Aissa

    2016-02-01

    A scored lithological map including 10 radiometric units is established through applying factor analysis approach to aerial spectrometric data of Area-1, Syrian desert, which includes Ur, eU, eTh, K%, eU/eTh, eU/K%, and eTh/K%. A model of four rotated factors F1, F2, F3, and F4 is adapted for representing 234,829 data measured points in Area-1, where 86% of total data variance is interpreted. A geological scored pseudo-section derived from the lithological scored map is established and analyzed in order to show the possible stratigraphic and structural traps for uranium occurrences associated with phosphate deposits in the studied Area-1. These identified traps presented in this paper need detailed investigation and must be necessarily followed and checked by ground validations and subsurface well logging, in order to locate the anomalous uranium occurrences and explore with more confidence and certitude their characteristics as a function of depth.

  5. Concurrent Label-Free Mass Spectrometric Analysis of Dystrophin Isoform Dp427 and the Myofibrosis Marker Collagen in Crude Extracts from mdx-4cv Skeletal Muscles

    Directory of Open Access Journals (Sweden)

    Sandra Murphy

    2015-09-01

    Full Text Available The full-length dystrophin protein isoform of 427 kDa (Dp427, the absence of which represents the principal abnormality in X-linked muscular dystrophy, is difficult to identify and characterize by routine proteomic screening approaches of crude tissue extracts. This is probably related to its large molecular size, its close association with the sarcolemmal membrane, and its existence within a heterogeneous glycoprotein complex. Here, we used a careful extraction procedure to isolate the total protein repertoire from normal versus dystrophic mdx-4cv skeletal muscles, in conjunction with label-free mass spectrometry, and successfully identified Dp427 by proteomic means. In contrast to a considerable number of previous comparative studies of the total skeletal muscle proteome, using whole tissue proteomics we show here for the first time that the reduced expression of this membrane cytoskeletal protein is the most significant alteration in dystrophinopathy. This agrees with the pathobiochemical concept that the almost complete absence of dystrophin is the main defect in Duchenne muscular dystrophy and that the mdx-4cv mouse model of dystrophinopathy exhibits only very few revertant fibers. Significant increases in collagens and associated fibrotic marker proteins, such as fibronectin, biglycan, asporin, decorin, prolargin, mimecan, and lumican were identified in dystrophin-deficient muscles. The up-regulation of collagen in mdx-4cv muscles was confirmed by immunofluorescence microscopy and immunoblotting. Thus, this is the first mass spectrometric study of crude tissue extracts that puts the proteomic identification of dystrophin in its proper pathophysiological context.

  6. Chemometric classification of gunshot residues based on energy dispersive X-ray microanalysis and inductively coupled plasma analysis with mass-spectrometric detection

    Energy Technology Data Exchange (ETDEWEB)

    Steffen, S. [Bundeskriminalamt (BKA), Forensic Science Institute KT23, Thaerstr. 11, D - 65193 Wiesbaden (Germany); Otto, M. [TU Bergakademie Freiberg (TU BAF), Institute for Analytical Chemistry, Leipziger Str. 29, D - 09599 Freiberg (Germany)], E-mail: matthias.otto@chemie.tu-freiberg.de; Niewoehner, L.; Barth, M. [Bundeskriminalamt (BKA), Forensic Science Institute KT23, Thaerstr. 11, D - 65193 Wiesbaden (Germany); Brozek-Mucha, Z. [Instytut Ekspertyz Sadowych (IES), Westerplatte St. 9, PL - 31-033 Krakow (Poland); Biegstraaten, J. [Nederlands Forensisch Instituut (NFI), Fysische Technologie, Laan van Ypenburg 6, NL-2497 GB Den Haag (Netherlands); Horvath, R. [Kriminalisticky a Expertizny Ustav (KEU PZ), Institute of Forensic Science, Sklabinska 1, SK - 812 72 Bratislava (Slovakia)

    2007-09-15

    A gunshot residue sample that was collected from an object or a suspected person is automatically searched for gunshot residue relevant particles. Particle data (such as size, morphology, position on the sample for manual relocation, etc.) as well as the corresponding X-ray spectra and images are stored. According to these data, particles are classified by the analysis-software into different groups: 'gunshot residue characteristic', 'consistent with gunshot residue' and environmental particles, respectively. Potential gunshot residue particles are manually checked and - if necessary - confirmed by the operating forensic scientist. As there are continuing developments on the ammunition market worldwide, it becomes more and more difficult to assign a detected particle to a particular ammunition brand. As well, the differentiation towards environmental particles similar to gunshot residue is getting more complex. To keep external conditions unchanged, gunshot residue particles were collected using a specially designed shooting device for the test shots revealing defined shooting distances between the weapon's muzzle and the target. The data obtained as X-ray spectra of a number of particles (3000 per ammunition brand) were reduced by Fast Fourier Transformation and subjected to a chemometric evaluation by means of regularized discriminant analysis. In addition to the scanning electron microscopy in combination with energy dispersive X-ray microanalysis results, isotope ratio measurements based on inductively coupled plasma analysis with mass-spectrometric detection were carried out to provide a supplementary feature for an even lower risk of misclassification.

  7. Timing of Holocene sea-level highstands by mass spectro-metric U-series ages of a coral reef from Leizhou Peninsula,South China Sea

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Systematic mass spectrometric 230Th ages are reported for a Porites coral reef terrace from Dengloujiao,Leizhou Peninsula, South China Sea. Seven episodes of coral growth were recognized in this terrace: 7125±96, 6764±29,5826±37, 5006±54, 2543±24, 1915±15, and 1513±22 calendar years before present (cal. aBP). 50% of the coral age population fall between 7200 and 6600 cal. aBP, marking post-glacial stabdization of global sea level. Considering the facts that ( i ) Dengloujiao reef fiat was measured at 1.6-2.5m above modern tidal datum plane; (ii) modern Porites corals in the South China Sea are living at least ~1 m below the modern tidal datum plane; (iii) the top 20-30 cm of the reef was eroded; and (iv) crustal subsidence in the region since mid-Holocene was negligible, we conclude that the above age groups record at least two major periods (7200-5000 and 2500-1500 cal. aBP) of high sea-level at least 2.9-3.8 m above the present-day level.

  8. Quick identification of xanthine oxidase inhibitor and antioxidant from Erycibe obtusifolia by a drug discovery platform composed of multiple mass spectrometric platforms and thin-layer chromatography bioautography.

    Science.gov (United States)

    Chen, Zhiyong; Tao, Hongxun; Liao, Liping; Zhang, Zijia; Wang, Zhengtao

    2014-08-01

    As a final step of the purine metabolism process, xanthine oxidase catalyzes the oxidation of hypoxanthine and xanthine into uric acid. Our research has demonstrated that Erycibe obtusifolia has xanthine oxidase inhibitory properties. The purpose of this paper is to describe a new strategy based on a combination of multiple mass spectrometric platforms and thin-layer chromatography bioautography for effectively screening the xanthine oxidase inhibitory and antioxidant properties of E. obtusifolia. This strategy was accomplished through the following steps. (i) Separate the extract of E. obtusifolia into fractions by an autopurification system controlled by liquid chromatography with mass spectrometry. (ii) Determine the active fractions of E. obtusifolia by thin-layer chromatography bioautography. (iii) Identify the structure of the main active compounds with the information provided by direct analysis in real time mass spectrometry. (iv) Calculate the IC50 value of each compound against xanthine oxidase using high-performance liquid chromatography. Using the caulis of E. obtusifolia as the experimental material, seven target peaks were screened out as xanthine oxidase inhibitors or antioxidants. Our screening strategy allows for rapid analysis of small molecules with almost no sample preparation and can be completed within a week, making it a useful assay to identify unstable compounds and provide the empirical foundation for E. obtusifolia as a natural remedy for gout and oxidative-stress-related diseases.

  9. Mass spectrometric investigations of alpha- and beta-cyclodextrin complexes with ortho-, meta- and para-coumaric acids by negative mode electrospray ionization.

    Science.gov (United States)

    Kralj, Bogdan; Smidovnik, Andrej; Kobe, Joze

    2009-01-01

    The mass spectrometric characterization of aqueous solutions of alpha- and beta-cyclodextrins (CDs) and o-, m- and p-coumaric acids (CAs) by negative ion electrospray ionization (ESI) indicates that the [CD+CA](-) ions were sourced from the inclusion complex present in solution and from the anion attached to CD molecules formed in the spray processes. The anion adducts formed in the spray process contribute significantly to the signal intensity of an ionized inclusion complex thus overestimating the calculated stability constant (K) of solution-phase complexes by one to two orders of magnitude. The relative intensities of anion adducts in mass spectra depend on the concentration ratio of the anion and the CD in spray droplets, while the relative intensity of the ionized inclusion complex depends on CD and CA concentrations in solutions and the value of K. Ion Mobility Spectrometry Mass Spectrometry [IMS-MS] measurements show that the collision cross-section (Omega) values of the [CD+CA](-) or [(CD)(2+)CA](2-) and [CD+CA](2) (2-) complex ions are 5-6% larger than or equal to CD(-) or [CD](2) (2-), respectively. Therefore, in the gas phase the anion adducts [CD+CA(-)] on cyclodextrin molecules possess the same conformations as the ionized inclusion complexes [CD+CA](-).

  10. Novel nerve-agent antidote design based on crystallographic and mass spectrometric analyses of tabun-conjugated acetylcholinesterase in complex with antidotes.

    Science.gov (United States)

    Ekström, F J; Astot, C; Pang, Y-P

    2007-09-01

    Organophosphorus compound-based nerve agents inhibit the essential enzyme acetylcholinesterase (AChE) causing acute toxicity and death. Clinical treatment of nerve-agent poisoning is to use oxime-based antidotes to reactivate the inhibited AChE. However, the nerve agent tabun is resistant to oximes. To design improved oximes, crystal structures of a tabun-conjugated AChE in complex with different oximes are needed to guide the structural modifications of known antidotes. However, this type of structure is extremely challenging to obtain because both deamidation of the tabun conjugate and reactivation of AChE occur during crystallographic experiments. Here we report, for the first time, the crystal structures of Ortho-7 and HLö-7 in complex with AChE that is conjugated to an intact tabun. These structures were determined by our new strategy of combining crystallographic and mass spectrometric analyses of AChE crystals. The results explain the relative reactivation potencies of the two oximes and offer insights into improving known medical antidotes.

  11. The role of peroxyl radicals in polyester degradation--a mass spectrometric product and kinetic study using the distonic radical ion approach.

    Science.gov (United States)

    Gervasoni, B D; Khairallah, G N; O'Hair, R A J; Wille, U

    2015-04-14

    Mass spectrometric techniques were used to obtain detailed insight into the reactions of peroxyl radicals with model systems of (damaged) polyesters. Using a distonic radical ion approach, it was shown that N-methylpyridinium peroxyl radical cations, Pyr(+)OO˙, do not react with non-activated C-H bonds typically present in polyesters that resist degradation. Structural damage in the polymer, for example small amounts of alkene moieties formed during the manufacturing process, is required to enable reaction with Pyr(+)OO˙, which proceeds with high preference through addition to the π system rather than via allylic hydrogen atom abstraction (kadd/kHAT > 20 for internal alkenes). This is due to the very fast and strongly exothermic subsequent fragmentation of the peroxyl-alkene radical adduct to epoxides and highly reactive Pyr(+)O˙, which both could promote further degradation of the polymer through non-radical and radical pathways. This work provides essential experimental support that the basic autoxidation mechanism is a too simplistic model to rationalize radical mediated degradation of polymers under ambient conditions.

  12. Mass-spectrometric identification of T-kininogen I/thiostatin as an acute-phase inflammatory protein suppressed by curcumin and capsaicin.

    Directory of Open Access Journals (Sweden)

    Bina Joe

    Full Text Available Curcumin and capsaicin are dietary xenobiotics with well-documented anti-inflammatory properties. Previously, the beneficial effect of these spice principles in lowering chronic inflammation was demonstrated using a rat experimental model for arthritis. The extent of lowering of arthritic index by the spice principles was associated with a significant shift in macrophage function favoring the reduction of pro-inflammatory molecules such as reactive oxygen species and production and release of anti-inflammatory metabolites of arachidonic acid. Beyond the cellular effects on macrophage function, oral administration of curcumin and capsaicin caused alterations in serum protein profiles of rats injected with adjuvant to develop arthritis. Specifically, a 72 kDa acidic glycoprotein, GpA72, which was elevated in pre-arthritic rats, was significantly lowered by feeding either curcumin or capsaicin to the rats. Employing the tandem mass spectrometric approach for direct sequencing of peptides, here we report the identification of GpA72 as T-kininogen I also known as Thiostatin. Since T-kininogen I is an early acute-phase protein, we additionally tested the efficiency of curcumin and capsaicin to mediate the inflammatory response in an acute phase model. The results demonstrate that curcumin and capsaicin lower the acute-phase inflammatory response, the molecular mechanism for which is, in part, mediated by pathways associated with the lowering of T-kininogen I.

  13. Gamma spectrometric and magnetic interpretation of Cabaçal copper deposit in Mato Grosso (Brazil): Implications for hydrothermal fluids remobilization

    Science.gov (United States)

    Ribeiro, Vanessa Biondo; Mantovani, Marta Silvia Maria

    2016-12-01

    The Cabaçal Au-Zn-Cu Deposit, Mato Grosso, Brazil, was explored between 1987 and 1991, when 869,279 tons of ore rich in Au and Cu have been extracted. The hydrothermal alteration in the Cabaçal mine suggests a volcanogenic genetic model in which hydrothermal centers generated sericitization, chloritization and silicification alterations at different stages. The hydrothermal alteration affects the radioelements in different ways, generating a characteristic gamma spectrometric signature for the affected area. The eTh/K ratio map evidenced that the hydrothermalized area extends beyond south limits of the Cabaçal gabbro dykes formation, which host Cabaçal and Santa Helena mines. Magnetic data over the region show the same behavior for this formation, indicating that the magnetic source extends in subsurface. This behavior was recovered by the 3D model inverted for the region, which recovered a positive apparent magnetic contrast associated with this body, with an increasing deepness to south. It is possible that the south subsurface portion of the magnetic source may contain economic concentrations of Au remobilized by hydrothermal fluids. However, to confirm this hypothesis it is necessary to develop geochemical and borehole analysis of the area.

  14. Gas chromatographic determination of acid herbicides in surface water samples with electron-capture detection and mass spectrometric confirmation

    NARCIS (Netherlands)

    Vink, M.; Poll, J.M. van der

    1996-01-01

    The development of a multi-residue method for the determination of eight polar acidic herbicides (MCPA, MCPB, mecoprop, 2,4-D, dichlorprop, bentazone, dicamba and dikegulac) in surface water is described. The method involves an off-line solid-phase extraction (SPE) procedure prior to instrumental an

  15. Concept for facilitating analyst-mediated interpretation of qualitative chromatographic-mass spectral data: an alternative to manual examination of extracted ion chromatograms.

    Science.gov (United States)

    Borges, Chad R

    2007-07-01

    A chemometrics-based data analysis concept has been developed as a substitute for manual inspection of extracted ion chromatograms (XICs), which facilitates rapid, analyst-mediated interpretation of GC- and LC/MS(n) data sets from samples undergoing qualitative batchwise screening for prespecified sets of analytes. Automatic preparation of data into two-dimensional row space-derived scatter plots (row space plots) eliminates the need to manually interpret hundreds to thousands of XICs per batch of samples while keeping all interpretation of raw data directly in the hands of the analyst-saving great quantities of human time without loss of integrity in the data analysis process. For a given analyte, two analyte-specific variables are automatically collected by a computer algorithm and placed into a data matrix (i.e., placed into row space): the first variable is the ion abundance corresponding to scan number x and analyte-specific m/z value y, and the second variable is the ion abundance corresponding to scan number x and analyte-specific m/z value z (a second ion). These two variables serve as the two axes of the aforementioned row space plots. In order to collect appropriate scan number (retention time) information, it is necessary to analyze, as part of every batch, a sample containing a mixture of all analytes to be tested. When pure standard materials of tested analytes are unavailable, but representative ion m/z values are known and retention time can be approximated, data are evaluated based on two-dimensional scores plots from principal component analysis of small time range(s) of mass spectral data. The time-saving efficiency of this concept is directly proportional to the percentage of negative samples and to the total number of samples processed simultaneously.

  16. UV-MALDI mass spectrometric quantitation of uracil based pesticides in fruit soft drinks along with matrix effects evaluation.

    Science.gov (United States)

    Ivanova, Bojidarka; Spiteller, Michael

    2014-02-01

    This study focused on the development of the accurate and precise quantitative method for the determination of pesticides bromacil (1), terbacil (2), lenacil (3), butafenacil (4) and flupropacil (5) in fruit based soft drinks. Three different types of drinks are bought from market; huddled orange fruit drink (100%) (I), red-oranges (II) and multivitamin drink containing strawberry, orange, banana and maracuja (III). Samples were analyzed "with" and "without" pulp utilizing LC-ESI (or APCI) MS/MS, HPLC-ESI-(or APCI)-MS/MS and UV-MALDI-Orbitrap-MS methods. The effect of high complexity of the food matrix on the analysis was discussed. Study focuses on the advantages of the UV-MALDI-Orbitrap-MS method compared to the traditionally involved GC alone or hybrid methods such as GC-MS and LC-MS/MS for quantification of pesticides in water and soft drinks. The developed method included the techniques performed for validation, calibration and standardization. The target pesticides are widely used for the treatment of citrus fruits and pineapples, but for soft drink products, there are still no clear regulations on pesticide residues limits. The matrix effects in the analysis of fruit drinks required implementation of the exact standard reference material corresponds to the variety of food matrices. This paper contributed to the broad analytical implementation of the UV-MALDI-Orbitrap-MS method in the quality control and assessment programs for monitoring of pesticide contamination in fruit based sodas.

  17. Quantitative Mass spectrometric Analysis of Ropivacaine and Bupivacaine in Authentic, Pharmaceutical and Spiked Human Plasma without Chromatographic Separation

    Directory of Open Access Journals (Sweden)

    Nahla N. Salama

    2009-01-01

    Full Text Available The present study employs time of flight mass spectrometry for quantitative analysis of the local anesthetic drugs ropivacaine and bupivacaine in authentic, pharmaceutical and spiked human plasma as well as in the presence of their impurities 2,6-dimethylaniline and alkaline degradation product. The method is based on time of flight electron spray ionization mass spectrometry technique without preliminary chromatographic separation and makes use of bupivacaine as internal standard for ropivacaine, which is used as internal standard for bupivacaine. A linear relationship between drug concentrations and the peak intensity ratio of ions of the analyzed substances is established. The method is linear from 23.8 to 2380.0 ng mL-1 for both drugs. The correlation coefficient was ≥0.996 in authentic and spiked human plasma. The average percentage recoveries in the ranges of 95.39%–102.75% was obtained. The method is accurate (% RE < 5% and reproducible with intra- and inter-assay precision (RSD% < 8.0%. The quantification limit is 23.8 ng mL-1 for both drugs. The method is not only highly sensitive and selective, but also simple and effective for determination or identification of both drugs in authentic and biological fluids. The method can be applied in purity testing, quality control and stability monitoring for the studied drugs.

  18. Simple Protein Complex Purification and Identification Method Suitable for High- throughput Mapping of Protein Interaction Networks

    Energy Technology Data Exchange (ETDEWEB)

    Markillie, Lye Meng; Lin, Chiann Tso; Adkins, Joshua N.; Auberry, Deanna L.; Hill, Eric A.; Hooker, Brian S.; Moore, Priscilla A.; Moore, Ronald J.; Shi, Liang; Wiley, H. S.; Kery, Vladimir

    2005-04-11

    Most of the current methods for purification and identification of protein complexes use endogenous expression of affinity tagged bait, tandem affinity tag purification of protein complexes followed by specific elution of complexes from beads, gel separation, in-gel digestion and mass spectrometric analysis of protein interactors. We propose a single affinity tag in vitro pulldown assay with denaturing elution, trypsin digestion in organic solvent and LC ESI MS/MS protein identification using SEQUEST analysis. Our method is simple, easy to scale up and automate thus suitable for high throughput mapping of protein interaction networks and functional proteomics.

  19. New High-Performance Liquid Chromatography Coupled Mass Spectrometry Method for the Detection of Lobster and Shrimp Allergens in Food Samples via Multiple Reaction Monitoring and Multiple Reaction Monitoring Cubed.

    Science.gov (United States)

    Korte, Robin; Monneuse, Jean-Marc; Gemrot, Elodie; Metton, Isabelle; Humpf, Hans-Ulrich; Brockmeyer, Jens

    2016-08-10

    Crustacean shellfish allergy ranks among the most frequent and severe food allergies for adults, demanding rugged and sensitive analytical routine methods. The objective of this study was therefore to develop a mass spectrometric approach for the detection of contamination with shrimp and lobster, two economically important types of crustaceans, in complex food matrices. Following a biomarker approach, we identified proteotypic peptides and developed a multiple reaction monitoring (MRM) method allowing for the identification and differentiation of shrimp and lobster in the food matrix at concentrations down to 0.1%. To further enhance sensitivity, we employed the MRM-cubed (MRM(3)) mode, which allowed us to detect crustaceans down to concentrations of 25 μg/g (crustacean/food, 0.0025%). We hereby present the first mass spectrometric method for the detection of shrimp and lobster in food matrices.

  20. Determination of plasticizers included in balloon by solid phase microextraction and gas chromatography with mass spectrometric detection.

    Energy Technology Data Exchange (ETDEWEB)

    Park, H.M.; Kim, J.H.; Ryu, J.Ch.; Kim, Y.M.; Lee, K.B. [Korea Institute of Science and Technology, Seoul (Korea)

    2001-02-01

    Solid-phase microextraction (SPME) with 85 {mu}m polyacrylate fiber, coupled to gas chromatography-mass spectrometry was used to analyze the plasticizers contained in balloon samples. The balloons were identified to be made of polyisoprene by IR spectroscopy. The plasticizers extracted from the balloon samples soaked in acetone-added water solvent for an hour were quantified by external standard method using nine kinds of plasticizers. The quantification method was validated for standard plasticizers in the range of 0.25-25 {mu}g/g. The detection limits were 0.11-0.38 {mu}g/g for different plasticizers. The RSDs for the reproducibility of this quantitation method were 3.7-14.2%. A few of balloons included risky level of plasticizer concerned as an endocrine disrupter, and it is necessary to regulate these products. (author). 10 refs., 3 tabs., 4 figs.