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Sample records for chemical ionization tandem

  1. Chemical ionization tandem mass spectrometer for the in situ measurement of methyl hydrogen peroxide

    International Nuclear Information System (INIS)

    A new approach for measuring gas-phase methyl hydrogen peroxide [(MHP) CH3OOH] utilizing chemical ionization mass spectrometry is presented. Tandem mass spectrometry is used to avoid mass interferences that hindered previous attempts to measure atmospheric CH3OOH with CF3O- clustering chemistry. CH3OOH has been successfully measured in situ using this technique during both airborne and ground-based campaigns. The accuracy and precision for the MHP measurement are a function of water vapor mixing ratio. Typical precision at 500 pptv MHP and 100 ppmv H2O is ±80 pptv (2 sigma) for a 1 s integration period. The accuracy at 100 ppmv H2O is estimated to be better than ±40%. Chemical ionization tandem mass spectrometry shows considerable promise for the determination of in situ atmospheric trace gas mixing ratios where isobaric compounds or mass interferences impede accurate measurements.

  2. Gas Chromatography/Atmospheric Pressure Chemical Ionization Tandem Mass Spectrometry for Fingerprinting the Macondo Oil Spill.

    Science.gov (United States)

    Lobodin, Vladislav V; Maksimova, Ekaterina V; Rodgers, Ryan P

    2016-07-01

    We report the first application of a new mass spectrometry technique (gas chromatography combined to atmospheric pressure chemical ionization tandem mass spectrometry, GC/APCI-MS/MS) for fingerprinting a crude oil and environmental samples from the largest accidental marine oil spill in history (the Macondo oil spill, the Gulf of Mexico, 2010). The fingerprinting of the oil spill is based on a trace analysis of petroleum biomarkers (steranes, diasteranes, and pentacyclic triterpanes) naturally occurring in crude oil. GC/APCI enables soft ionization of petroleum compounds that form abundant molecular ions without (or little) fragmentation. The ability to operate the instrument simultaneously in several tandem mass spectrometry (MS/MS) modes (e.g., full scan, product ion scan, reaction monitoring) significantly improves structural information content and sensitivity of analysis. For fingerprinting the oil spill, we constructed diagrams and conducted correlation studies that measure the similarity between environmental samples and enable us to differentiate the Macondo oil spill from other sources. PMID:27281271

  3. Quantitative analysis of adenosine using Liquid Chromatography/Atmospheric Pressure Chemical Ionization - tandem Mass Spectrometry (LC/APCI-MS/MS)

    OpenAIRE

    Van Dycke, Annelies; Verstraete, Alain; Pil, Kristof; Raedt, Robrecht; Vonck, Kristl; Boison, Detlev; Boon, Paul

    2010-01-01

    Adenosine-secreting cellular brain implants constitute a promising therapeutic approach for the treatment of epilepsy. To engineer neural stem cells for therapeutic adenosine delivery, a reliable and fast analytical method is necessary to quantify cell-based adenosine release. Here we describe the development, optimization and validation of adenosine measurement using liquid chromatography – atmospheric pressure chemical ionizationtandem mass spectrometry (LC-APCI-MS/MS). LC-MS/MS in posit...

  4. Regioisomers of octanoic acid-containing structured triacylglycerols analyzed by tandem mass spectrometry using ammonia negative ion chemical ionization

    DEFF Research Database (Denmark)

    Kurvinen, J.P.; Mu, Huiling; Kallio, H.;

    2001-01-01

    Tandem mass spectrometry based on ammonia negative ion chemical ionization and sample introduction via direct exposure probe was applied to analysis of regioisomeric structures of octanoic acid containing structured triacylglycerols (TAG) of type MML, MLM, MLL, and LML (M, medium-chain fatty acid......; L, long-chain fatty acid). Collision-induced dissociation of deprotonated parent TAG with argon was used to produce daughter ion spectra with appropriate fragmentation patterns for structure determination. Fatty acids constituting the TAG molecule were identified according to [RCO2](-) ions in the...... daughter ion spectra. With the standard curve for ratios of [M - H - RCO2H - 100](-) ions corresponding to each [RCO2](-) ion, determined with known mixtures of sn-1/3 and sn-2 regioisomers of structured TAG, it was possible to determine the proportions of different regioisomers in unknown samples. The...

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

    Science.gov (United States)

    Thomas, Aurélien; Widmer, Christèle; Hopfgartner, Gérard; Staub, Christian

    2007-11-01

    The present work describes a fast gas chromatography/negative-ion chemical ionization tandem mass spectrometric assay (Fast GC/NICI-MS/MS) for analysis of tetrahydrocannabinol (THC), 11-hydroxy-tetrahydrocannabinol (THC-OH) and 11-nor-9-carboxy-tetrahydrocannabinol (THC-COOH) in whole blood. The cannabinoids were extracted from 500 microL of whole blood by a simple liquid-liquid extraction (LLE) and then derivatized by using trifluoroacetic anhydride (TFAA) and hexafluoro-2-propanol (HFIP) as fluorinated agents. Mass spectrometric detection of the analytes was performed in the selected reaction-monitoring mode on a triple quadrupole instrument after negative-ion chemical ionization. The assay was found to be linear in the concentration range of 0.5-20 ng/mL for THC and THC-OH, and of 2.5-100 ng/mL for THC-COOH. Repeatability and intermediate precision were found less than 12% for all concentrations tested. Under standard chromatographic conditions, the run cycle time would have been 15 min. By using fast conditions of separation, the assay analysis time has been reduced to 5 min, without compromising the chromatographic resolution. Finally, a simple approach for estimating the uncertainty measurement is presented. PMID:17913432

  6. Diclofenac in municipal wastewater treatment plant: quantification using laser diode thermal desorption--atmospheric pressure chemical ionization--tandem mass spectrometry approach in comparison with an established liquid chromatography-electrospray ionization-tandem mass spectrometry method.

    Science.gov (United States)

    Lonappan, Linson; Pulicharla, Rama; Rouissi, Tarek; Brar, Satinder K; Verma, Mausam; Surampalli, Rao Y; Valero, José R

    2016-02-12

    Diclofenac (DCF), a prevalent non-steroidal anti-inflammatory drug (NSAID) is often detected in wastewater and surface water. Analysis of the pharmaceuticals in complex matrices is often laden with challenges. In this study a reliable, rapid and sensitive method based on laser diode thermal desorption/atmospheric pressure chemical ionization (LDTD/APCI) coupled with tandem mass spectrometry (MS/MS) has been developed for the quantification of DCF in wastewater and wastewater sludge. An established conventional LC-ESI-MS/MS (liquid chromatography-electrospray ionization-tandem mass spectrometry) method was compared with LDTD-APCI-MS/MS approach. The newly developed LDTD-APCI-MS/MS method reduced the analysis time to 12s in lieu of 12 min for LC-ESI-MS/MS method. The method detection limits for LDTD-APCI-MS/MS method were found to be 270 ng L(-1) (LOD) and 1000 ng L(-1) (LOQ). Furthermore, two extraction procedures, ultrasonic assisted extraction (USE) and accelerated solvent extraction (ASE) for the extraction of DCF from wastewater sludge were compared and ASE with 95.6 ± 7% recovery was effective over USE with 86 ± 4% recovery. The fate and partitioning of DCF in wastewater (WW) and wastewater sludge (WWS) in wastewater treatment plant was also monitored at various stages of treatment in Quebec Urban community wastewater treatment plant. DCF exhibited affinity towards WW than WWS with a presence about 60% of DCF in WW in contrary with theoretical prediction (LogKow=4.51). PMID:26805597

  7. Potential of gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry for screening and quantification of hexabromocyclododecane.

    Science.gov (United States)

    Sales, Carlos; Portolés, Tania; Sancho, Juan Vicente; Abad, Esteban; Ábalos, Manuela; Sauló, Jordi; Fiedler, Heidelore; Gómara, Belén; Beltrán, Joaquim

    2016-01-01

    A fast method for the screening and quantification of hexabromocyclododecane (sum of all isomers) by gas chromatography using a triple quadrupole mass spectrometer with atmospheric pressure chemical ionization (GC-APCI-QqQ) is proposed. This novel procedure makes use of the soft atmospheric pressure chemical ionization source, which results in less fragmentation of the analyte than by conventional electron impact (EI) and chemical ionization (CI) sources, favoring the formation of the [M - Br](+) ion and, thus, enhancing sensitivity and selectivity. Detection was based on the consecutive loses of HBr from the [M - Br](+) ion to form the specific [M - H5Br6](+) and [M - H4Br5](+) ions, which were selected as quantitation (Q) and qualification (q) transitions, respectively. Parameters affecting ionization and MS/MS detection were studied. Method performance was also evaluated; calibration curves were found linear from 1 pg/μL to 100 pg/μL for the total HBCD concentration; instrumental detection limit was estimated to be 0.10 pg/μL; repeatability and reproducibility, expressed as relative standard deviation, were better than 7% in both cases. The application to different real samples [polyurethane foam disks (PUFs), food, and marine samples] pointed out a rapid way to identify and allow quantification of this compound together with a number of polybrominated diphenyl ethers (BDE congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two other novel brominated flame retardants [i.e., decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)] because of their presence in the same fraction when performing the usual sample treatment. PMID:26554601

  8. Chemical Investigation of Saponins in Different Parts of Panax notoginseng by Pressurized Liquid Extraction and Liquid Chromatography-Electrospray Ionization-Tandem Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Si-Jia Hong

    2012-05-01

    Full Text Available A pressurized liquid extraction (PLE and high performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS method was developed for the qualitative determination of saponins in different parts of P. notoginseng, including rhizome, root, fibre root, seed, stem, leaf and flower. The samples were extracted using PLE. The analysis was achieved on a Zorbax SB-C18 column with gradient elution of acetonitrile and 8 mM aqueous ammonium acetate as mobile phase. The mass spectrometer was operated in the negative ion mode using the electrospray ionization, and a collision induced dissociation (CID experiment was also carried out to aid the identification of compounds. Forty one saponins were identified in different parts of P. notoginseng according to the fragmentation patterns and literature reports, among them, 21 saponins were confirmed by comparing the retention time and ESI-MS data with those of standard compounds. The results showed that the chemical characteristics were obviously diverse in different parts of P. notoginseng, which is helpful for pharmacological evaluation and quality control of P. notoginseng.

  9. Potential of atmospheric pressure chemical ionization source in gas chromatography tandem mass spectrometry for the screening of urinary exogenous androgenic anabolic steroids.

    Science.gov (United States)

    Raro, M; Portolés, T; Pitarch, E; Sancho, J V; Hernández, F; Garrostas, L; Marcos, J; Ventura, R; Segura, J; Pozo, O J

    2016-02-01

    The atmospheric pressure chemical ionization (APCI) source for gas chromatography-mass spectrometry analysis has been evaluated for the screening of 16 exogenous androgenic anabolic steroids (AAS) in urine. The sample treatment is based on the strategy currently applied in doping control laboratories i.e. enzymatic hydrolysis, liquid-liquid extraction (LLE) and derivatization to form the trimethylsilyl ether-trimethylsilyl enol ether (TMS) derivatives. These TMS derivatives are then analyzed by gas chromatography tandem mass spectrometry using a triple quadrupole instrument (GC-QqQ MS/MS) under selected reaction monitoring (SRM) mode. The APCI promotes soft ionization with very little fragmentation resulting, in most cases, in abundant [M + H](+) or [M + H-2TMSOH](+) ions, which can be chosen as precursor ions for the SRM transitions, improving in this way the selectivity and sensitivity of the method. Specificity of the transitions is also of great relevance, as the presence of endogenous compounds can affect the measurements when using the most abundant ions. The method has been qualitatively validated by spiking six different urine samples at two concentration levels each. Precision was generally satisfactory with RSD values below 25 and 15% at the low and high concentration level, respectively. Most the limits of detection (LOD) were below 0.5 ng mL(-1). Validation results were compared with the commonly used method based on the electron ionization (EI) source. EI analysis was found to be slightly more repeatable whereas lower LODs were found for APCI. In addition, the applicability of the developed method has been tested in samples collected after the administration of 4-chloromethandienone. The highest sensitivity of the APCI method for this compound, allowed to increase the period in which its administration can be detected. PMID:26772132

  10. A high-performance liquid chromatographic-atmospheric pressure chemical ionization-tandem mass spectrometric method for determination of risperidone and 9-hydroxyrisperidone in human plasma.

    Science.gov (United States)

    Moody, David E; Laycock, John D; Huang, Wei; Foltz, Rodger L

    2004-09-01

    Risperidone, a benzisoxazole derivative, is an antipsychotic agent used for the treatment of schizophrenia. We developed a liquid chromatographic-atmospheric pressure chemical ionization-tandem mass spectrometric (LC-APCI-MS-MS) method with improved sensitivity, selectivity, and dynamic range for determination of risperidone and 9-hydroxyrisperidone in human plasma. A structural analogue of risperidone, RO68808 (5 ng/mL), is added as the internal standard to 1 mL of human plasma. Plasma is made basic, extracted with pentane/methylene chloride (3:1), the organic phase evaporated to dryness, and the residue is reconstituted in water with 0.1% formic acid/acetonitrile (20:1). For LC-MS-MS analysis, a Metachem Inertsel HPLC column (2.1 x 150 mm, 5-microm particle size) is connected to a Finnigan TSQ7000 tandem MS via the Finnigan API interface. Both electrospray (ESI) and APCI produced predominantly MH(+) ions for the two analytes and the internal standard. Ions detected by selected reaction monitoring correspond to the following transitions: m/z 411 to 191 for risperidone, m/z 427 to 207 for 9-hydroxyrisperidone, and m/z 421 to 201 for the internal standard. APCI provided a larger dynamic range (0.1 to 25 ng/mL) and better precision and accuracy than ESI. Intrarun accuracy and precision determined at 0.1, 0.25, 2.5, and 15 ng/mL were within 12% of target with %CVs not exceeding 10.9%. Interrun accuracy and precision determined at the same concentrations were within 9.6% of target with %CVs not exceeding 6.7%. Analytes were stable in plasma after 24 h at room temperature, 2 freeze-thaw cycles, and 490 days at -20 degrees C. PMID:15516302

  11. Determination of talinolol in human plasma using automated on-line solid phase extraction combined with atmospheric pressure chemical ionization tandem mass spectrometry.

    Science.gov (United States)

    Bourgogne, Emmanuel; Grivet, Chantal; Hopfgartner, Gérard

    2005-06-01

    A specific LC-MS/MS assay was developed for the automated determination of talinolol in human plasma, using on-line solid phase extraction system (prospekt 2) combined with atmospheric pressure chemical ionization (APCI) tandem mass spectrometry. The method involved simple precipitation of plasma proteins with perchloric acid (contained propranolol) as the internal standard (IS) and injection of the supernatant onto a C8 End Capped (10 mmx2 mm) cartridge without any evaporation step. Using the back-flush mode, the analytes were transferred onto an analytical column (XTerra C18, 50 mmx4.6 mm) for chromatographic separation and mass spectrometry detection. One of the particularities of the assay is that the SPE cartridge is used as a column switching device and not as an SPE cartridge. Therefore, the same SPE cartridge could be used more than 28 times, significantly reducing the analysis cost. APCI ionization was selected to overcome any potential matrix suppression effects because the analyte and IS co-eluted. The mean precision and accuracy in the concentration range 2.5-200 ng/mL was found to be 103% and 7.4%, respectively. The data was assessed from QC samples during the validation phase of the assay. The lower limit of quantification was 2.5 ng/mL, using a 250 microL plasma aliquot. The LC-MS/MS method provided the requisite selectivity, sensitivity, robustness accuracy and precision to assess pharmacokinetics of the compound in several hundred human plasma samples. PMID:15866498

  12. Analysis of vitamin K1 in fruits and vegetables using accelerated solvent extraction and liquid chromatography tandem mass spectrometry with atmospheric pressure chemical ionization.

    Science.gov (United States)

    Jäpelt, Rie Bak; Jakobsen, Jette

    2016-02-01

    The objective of this study was to develop a rapid, sensitive, and specific analytical method to study vitamin K1 in fruits and vegetables. Accelerated solvent extraction and solid phase extraction was used for sample preparation. Quantification was done by liquid chromatography tandem mass spectrometry with atmospheric pressure chemical ionization in selected reaction monitoring mode with deuterium-labeled vitamin K1 as an internal standard. The precision was estimated as the pooled estimate of three replicates performed on three different days for spinach, peas, apples, banana, and beetroot. The repeatability was 5.2% and the internal reproducibility was 6.2%. Recovery was in the range 90-120%. No significant difference was observed between the results obtained by the present method and by a method using the same principle as the CEN-standard i.e. liquid-liquid extraction and post-column zinc reduction with fluorescence detection. Limit of quantification was estimated to 0.05 μg/100g fresh weight. PMID:26304366

  13. Carbamazepine in municipal wastewater and wastewater sludge: ultrafast quantification by laser diode thermal desorption-atmospheric pressure chemical ionization coupled with tandem mass spectrometry.

    Science.gov (United States)

    Mohapatra, D P; Brar, S K; Tyagi, R D; Picard, P; Surampalli, R Y

    2012-09-15

    In this study, the distribution of the anti-epileptic drug carbamazepine (CBZ) in wastewater (WW) and aqueous and solid phases of wastewater sludge (WWS) was carried out. A rapid and reliable method enabling high-throughput sample analysis for quicker data generation, detection, and monitoring of CBZ in WW and WWS was developed and validated. The ultrafast method (15s per sample) is based on the laser diode thermal desorption-atmospheric pressure chemical ionization (LDTD-APCI) coupled to tandem mass spectrometry (MS/MS). The optimization of instrumental parameters and method application for environmental analysis are presented. The performance of the novel method was evaluated by estimation of extraction recovery, linearity, precision and detection limit. The method detection limits was 12 ng L(-1) in WW and 3.4 ng g(-1) in WWS. The intra- and inter-day precisions were 8% and 11% in WW and 6% and 9% in WWS, respectively. Furthermore, three extraction methods, ultrasonic extraction (USE), microwave-assisted extraction (MAE) and accelerated solvent extraction (ASE) with three different solvent condition such as methanol, acetone and acetonitrile:ethyle acetate (5:1, v/v) were compared on the basis of procedural blank and method recovery. Overall, ASE showed the best extraction efficiency with methanol as compared to USE and MAE. Furthermore, the quantification of CBZ in WW and WWS samples showed the presence of contaminant in all stages of the treatment plant. PMID:22967548

  14. Sensitive and comprehensive detection of chemical warfare agents in air by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow introduction.

    Science.gov (United States)

    Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Yamashiro, Shigeharu; Sano, Yasuhiro; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Sekiguchi, Hiroyuki; Iura, Kazumitsu; Nagashima, Hisayuki; Nagoya, Tomoki; Tsuge, Kouichiro; Ohsawa, Isaac; Okumura, Akihiko; Takada, Yasuaki; Ezawa, Naoya; Watanabe, Susumu; Hashimoto, Hiroaki

    2014-05-01

    A highly sensitive and specific real-time field-deployable detection technology, based on counterflow air introduction atmospheric pressure chemical ionization, has been developed for a wide range of chemical warfare agents (CWAs) comprising gaseous (two blood agents, three choking agents), volatile (six nerve gases and one precursor agent, five blister agents), and nonvolatile (three lachrymators, three vomiting agents) agents in air. The approach can afford effective chemical ionization, in both positive and negative ion modes, for ion trap multiple-stage mass spectrometry (MS(n)). The volatile and nonvolatile CWAs tested provided characteristic ions, which were fragmented into MS(3) product ions in positive and negative ion modes. Portions of the fragment ions were assigned by laboratory hybrid mass spectrometry (MS) composed of linear ion trap and high-resolution mass spectrometers. Gaseous agents were detected by MS or MS(2) in negative ion mode. The limits of detection for a 1 s measurement were typically at or below the microgram per cubic meter level except for chloropicrin (submilligram per cubic meter). Matrix effects by gasoline vapor resulted in minimal false-positive signals for all the CWAs and some signal suppression in the case of mustard gas. The moisture level did influence the measurement of the CWAs. PMID:24678766

  15. Phenolic Compounds of Pinus brutia Ten.: Chemical Investigation and Quantitative Analysis Using an Ultra-Performance Liquid Chromatography Tandem Mass Spectrometry with Electrospray Ionization Source

    OpenAIRE

    İbrahim Kıvrak; Şeyda Kıvrak; Mansur Harmandar; Yunus Çetintaş

    2013-01-01

    In this study, phenolic content of Pinus brutia ’s bark was examined using an ultra-performance liquid chromatography tandem mass spectrometry with electrospray ionization source (UPLC-ESI-MS/MS) working in multiple reaction monitoring mode. U ltrasonic extraction method with 50% ethanol solution was used for the extraction of bark. The bark of Pinus brutia consisted of 15 compounds: gallic acid, gentisic acid, protocatechuic acid, 4-hydroxy benzoic acid, catechin hydrate, vanillic acid, caff...

  16. Chemical Investigation of Saponins in Different Parts of Panax notoginseng by Pressurized Liquid Extraction and Liquid Chromatography-Electrospray Ionization-Tandem Mass Spectrometry

    OpenAIRE

    Si-Jia Hong; Peng Li; Yi-Tao Wang; Shao-Ping Li; Qing-Wen Zhang; Jian-Bo Wan

    2012-01-01

    A pressurized liquid extraction (PLE) and high performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS) method was developed for the qualitative determination of saponins in different parts of P. notoginseng, including rhizome, root, fibre root, seed, stem, leaf and flower. The samples were extracted using PLE. The analysis was achieved on a Zorbax SB-C18 column with gradient elution of acetonitrile and 8 mM aqueous ammonium acet...

  17. Quantitative determination of dexamethasone in bovine milk by liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    Science.gov (United States)

    Cherlet, Marc; De Baere, Siegrid; De Backer, Patrick

    2004-06-01

    Dexamethasone (DXM) is a synthetic glucocorticoid that is authorized for therapeutic use in veterinary medicine. The European Community (EC) fixed a maximum residue limit (MRL) at 2ng/g for liver, 0.75ng/g for muscle and kidney tissues, and 0.3ng/ml for milk, while its use as growth-promoter is completely banned. The purpose of this study was to develop and validate a simple and reliable method to determine DXM residues in bovine milk. Milk proteins were removed by the addition of concentrated trichloroacetic acid and paper filtration. Solid-phase extraction clean-up on a C18 reversed phase column was performed to obtain an extract suitable for liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. Chromatographic separation of DXM and the internal standard desoximetasone, was achieved on a PLRP-S polymeric reversed phase column, using a mixture of 0.1% (v/v) acetic acid in water (mobile phase A) and acetonitrile (mobile phase B) as the mobile phases. They were identified using the MS/MS detection technique, and were subsequently quantified. The method has been validated according to the requirements of the EC at 0.15, 0.30 and 0.60ng/ml (being half the MRL, the MRL and double the MRL levels fixed by the EC). Calibration graphs were prepared in the 0.15-5ng/ml range and good linearity was achieved (r>or=0.99 and goodness of fit

  18. Gas chromatography-tandem mass spectrometry with atmospheric pressure chemical ionization for fluorotelomer alcohols and perfluorinated sulfonamides determination.

    Science.gov (United States)

    Portolés, Tania; Rosales, Luis E; Sancho, Juan V; Santos, F Javier; Moyano, Encarnación

    2015-09-25

    Ionization and in source-fragmentation behavior of four fluorotelomer alcohols (FTOH) (4:2 FTOH, 6:2 FTOH, 8:2 FTOH and 10:2 FTOH) and four N-alkyl fluorooctane sulfonamides/-ethanols (N-MeFOSA, N-EtFOSA, N-MeFOSE and N-EtFOSE) by APCI has been studied and compared with the traditionally used EI and CI. Protonated molecule was the base peak of the APCI spectrum in all cases giving the possibility of selecting it as a precursor ion for MS/MS experiments. Following, CID fragmentation showed common product ions for all FOSAs/FOSEs (C4F7 and C3F5). Nevertheless, the different functionality gave characteristic pattern fragmentations. For instance, FTOHs mainly loss H2O+HF, FOSAs showed the losses of SO2 and HF while FOSEs showed the losses of H2O and SO2. Linearity, repeatability and LODs have been studied obtaining instrumental LODs between 1 and 5fg. Finally, application to river water and influent and effluent waste water samples has been carried out in order to investigate the improvements in detection capabilities of this new source in comparison with the traditionally used EI/CI sources. Matrix effects in APCI have been evaluated in terms of signal enhancement/suppression when comparing standards in solvent and matrix. No matrix effects were observed and concentrations found in samples were in the range of 1-100pgL(-1) far below the LODs achieved with methods previously reported. Unknown related perfluoroalkyl substances, as methyl-sulfone and methyl-sulfoxide analogues for FTOHs, were also discovered and tentatively identified. PMID:26298605

  19. Determination of eight nitrosamines in water at the ng L{sup -1} levels by liquid chromatography coupled to atmospheric pressure chemical ionization tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ripolles, Cristina; Pitarch, Elena; Sancho, Juan V.; Lopez, Francisco J. [Research Institute for Pesticides and Water, University Jaume I, Avda. Sos Baynat, E-12071 Castellon (Spain); Hernandez, Felix, E-mail: felix.hernandez@qfa.uji.es [Research Institute for Pesticides and Water, University Jaume I, Avda. Sos Baynat, E-12071 Castellon (Spain)

    2011-09-19

    Highlights: {center_dot} Eight N-nitrosamines in water by LC(APCI)MS/MS QqQ analysis. {center_dot} Validation at two levels: 10 ng L{sup -1} (LOQ) and 100 ng L{sup -1} in drinking water. {center_dot} Developed method applied to different types of water samples. {center_dot} NDMA was the analyte more frequently detected and at the highest concentration levels. - Abstract: In this work, we have developed a sensitive method for detection and quantification of eight N-nitrosamines, N-nitrosodimethylamine (NDMA), N-nitrosomorpholine (NMor), N-nitrosomethylethylamine (NMEA), N-nitrosopirrolidine (NPyr), N-nitrosodiethylamine (NDEA), N-nitrosopiperidine (NPip), N-nitroso-n-dipropylamine (NDPA) and N-nitrosodi-n-butylamine (NDBA) in drinking water. The method is based on liquid chromatography coupled to tandem mass spectrometry, using atmospheric pressure chemical ionization (APCI) in positive mode with a triple quadrupole analyzer (QqQ). The simultaneous acquisition of two MS/MS transitions in selected reaction monitoring mode (SRM) for each compound, together with the evaluation of their relative intensity, allowed the simultaneous quantification and reliable identification in water at ppt levels. Empirical formula of the product ions selected was confirmed by UHPLC-(Q)TOF MS accurate mass measurements from reference standards. Prior to LC-MS/MS QqQ analysis, a preconcentration step by off-line SPE using coconut charcoal EPA 521 cartridges (by passing 500 mL of water sample) was necessary to improve the sensitivity and to meet regulation requirements. For accurate quantification, two isotope labelled nitrosamines (NDMA-d{sub 6} and NDPA-d{sub 14}) were added as surrogate internal standards to the samples. The optimized method was validated at two concentration levels (10 and 100 ng L{sup -1}) in drinking water samples, obtaining satisfactory recoveries (between 90 and 120%) and precision (RSD < 20%). Limits of detection were found to be in the range of 1-8 ng L{sup -1

  20. Analysis of vitamin K-1 in fruits and vegetables using accelerated solvent extraction and liquid chromatography tandem mass spectrometry with atmospheric pressure chemical ionization

    DEFF Research Database (Denmark)

    Jäpelt, Rie Bak; Jakobsen, Jette

    2016-01-01

    spectrometry with atmospheric pressure chemical ionization in selected reaction monitoring mode with deuterium-labeled vitamin K1 as an internal standard. The precision was estimated as the pooled estimate of three replicates performed on three different days for spinach, peas, apples, banana, and beetroot...

  1. Phenolic Compounds of Pinus brutia Ten.: Chemical Investigation and Quantitative Analysis Using an Ultra-Performance Liquid Chromatography Tandem Mass Spectrometry with Electrospray Ionization Source

    Directory of Open Access Journals (Sweden)

    İbrahim Kıvrak

    2013-08-01

    Full Text Available In this study, phenolic content of Pinus brutia ’s bark was examined using an ultra-performance liquid chromatography tandem mass spectrometry with electrospray ionization source (UPLC-ESI-MS/MS working in multiple reaction monitoring mode. U ltrasonic extraction method with 50% ethanol solution was used for the extraction of bark. The bark of Pinus brutia consisted of 15 compounds: gallic acid, gentisic acid, protocatechuic acid, 4-hydroxy benzoic acid, catechin hydrate, vanillic acid, caffeic acid, vanillin, p-coumaric acid, ferulic acid, myricetin, resveratrol, luteolin, naringenin, kaempferol. Major compound detected was catechin hydrate (28.305 mg 100 g -1 extract. The phenolic compounds of Pinus brutia extract and pycnogenol were compared, and it is shown that both of them consisted of considerable amount of phenolic compounds.

  2. Diagnostic ion filtering strategy for chemical characterization of Guge Fengtong Tablet with high-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

    Science.gov (United States)

    Zeng, Su-Ling; Liu, Xin-Guang; Lai, Chang-Jiang-Sheng; Liu, E-Hu; Li, Ping

    2015-05-01

    The present study was designed to characterize the chemical constituents of Guge Fengtong Tablet (GGFTT). Based on the chromatographic retention behavior, fragmentation pathways of chemical components and the published literatures, a diagnostic ion filtering strategy with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (HPLC-ESI-Q-TOF/MS) was established to identify the multiple bioactive constituents of GGFTT. The rapid identification of forty-seven components, including 18 phenolic acids, 8 saponins, 14 gingerol-related compounds, and 7 diarylhepatonoids, was accomplished using this newly developed method. The coupling of HPLC-ESI-Q-TOF/MS with the diagnostic ion filtering strategy was useful and efficient for the in-depth structural elucidation of chemical compounds of GGFTT. PMID:25986289

  3. Evaluation of the capabilities of atmospheric pressure chemical ionization source coupled to tandem mass spectrometry for the determination of dioxin-like polychlorobiphenyls in complex-matrix food samples.

    Science.gov (United States)

    Portolés, T; Sales, C; Abalos, M; Sauló, J; Abad, E

    2016-09-21

    The use of the novel atmospheric pressure chemical ionization (APCI) source for gas chromatography (GC) coupled to triple quadrupole using tandem mass spectrometry (MS/MS) and its potential for the simultaneous determination of the 12 dioxin-like polychlorobiphenyls (DL-PCBs) in complex food and feed matrices has been evaluated. In first place, ionization and fragmentation behavior of DL-PCBs on the APCI source under charge transfer conditions has been studied followed by their fragmentation in the collision cell. Linearity, repeatability and sensitivity have been studied obtaining instrumental limits of detection and quantification of 0.0025 and 0.005 pg μL(-1) (2.5 and 5 fg on column) respectively for every DL-PCB. Finally, application to real samples has been carried out and DL-PCB congeners (PCB 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189) have been detected in the different samples in the range of 0.40-10000 pg g(-1). GC-(APCI)MS/MS has been proved as a suitable alternative to the traditionally accepted confirmation method based on the use of high resolution mass spectrometry and other triple quadrupole tandem mass spectrometry techniques operating with electron ionization. The development of MS/MS methodologies for the analysis of dioxins and DL-PCBs is nowadays particularly important, since this technique was included as a confirmatory method in the present European Union regulations that establish the requirements for the determination of these compounds in food and feed matrices. PMID:27590550

  4. Novel analytical approach for brominated flame retardants based on the use of gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry with emphasis in highly brominated congeners.

    Science.gov (United States)

    Portolés, Tania; Sales, Carlos; Gómara, Belén; Sancho, Juan Vicente; Beltrán, Joaquim; Herrero, Laura; González, María José; Hernández, Félix

    2015-10-01

    The analysis of brominated flame retardants (BFRs) commonly relies on the use of gas chromatography coupled to mass spectrometry (GC-MS) operating in electron ionization (EI) and electron capture negative ionization (ECNI) modes using quadrupole, triple quadrupole, ion trap, and magnetic sector analyzers. However, these brominated contaminants are examples of compounds for which a soft and robust ionization technique might be favorable since they show high fragmentation in EI and low specificity in ECNI. In addition, the low limits of quantification (0.01 ng/g) required by European Commission Recommendation 2014/118/EU on the monitoring of traces of BFRs in food put stress on the use of highly sensitive techniques/methods. In this work, a new approach for the extremely sensitive determination of BFRs taking profit of the potential of atmospheric pressure chemical ionization (APCI) combined with GC and triple quadrupole (QqQ) mass analyzer is proposed. The objective was to explore the potential of this approach for the BFRs determination in samples at pg/g levels, taking marine samples and a cream sample as a model. Ionization and fragmentation behavior of 14 PBDEs (congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two novel BFRs, decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), in the GC-APCI-MS system has been investigated. The formation of highly abundant (quasi) molecular ion was the main advantage observed in relation to EI. Thus, a notable improvement in sensitivity and specificity was observed when using it as precursor ion in tandem MS. The improved detectability (LODs < 10 fg) achieved when using APCI compared to EI has been demonstrated, which is especially relevant for highly brominated congeners. Analysis of samples from an intercomparison exercise and samples from the marine field showed the potential of this approach for the reliable identification and quantification at very low

  5. Simultaneous extraction of acetylsalicylic acid and salicylic acid from human plasma and simultaneous estimation by liquid chromatography and atmospheric pressure chemical ionization/tandem mass spectrometry detection. Application to a pharmacokinetic study.

    Science.gov (United States)

    Nirogi, Ramakrishna; Kandikere, Vishwottam; Mudigonda, Koteshwara; Ajjala, Devender; Suraneni, Ramakrishna; Thoddi, Parthasarathi

    2011-01-01

    A simple analytical method using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in atmospheric chemical ionization mode (APCI) for the simultaneous estimation of acetylsalicylic acid (ASA, CAS 50-78-2) and its active metabolite salicylic acid (SA, CAS 69-72-7) in human plasma has been developed and validated. ASA and SA were analyzed simultaneously despite differences in plasma concentration ranges of ASA and SA after oral administration of ASA. In spite of having different chemical, ionization and chromatographic properties, ASA and SA were extracted simultaneously from the plasma sample using acetonitrile protein precipitation followed by liquid-liquid extraction. The analytes were separated on a reversed phase column with rapid gradient program using mobile phase consisting of ammonium acetate buffer and methanol. The structural analogue diclofenac was used as an internal standard. The multiple reaction monitoring (MRM) transitions m/z 179 --> 137 for ASA, m/z 137 --> 65 for SA and m/z 294 --> 250 for IS were used. The assay exhibited a linear dynamic range of 0.02-10 microg/mL for ASA and 0.1-50 microg/mL for SA. The between-batch precision (%CV) ranged from 2.1 to 7.9% for ASA and from 0.2 to 5.2% for SA. The between-batch accuracy ranged from 95.4 to 96.7% for ASA and from 94.6 to 111.3% for SA. The validated method was successfully applied for the evaluation of pharmacokinetics of ASA after single oral administration of 650 mg test formulation versus two 325 mg reference formulations of ASA in human subjects. PMID:21755814

  6. Development of a new multi-residue laser diode thermal desorption atmospheric pressure chemical ionization tandem mass spectrometry method for the detection and quantification of pesticides and pharmaceuticals in wastewater samples.

    Science.gov (United States)

    Boisvert, Michel; Fayad, Paul B; Sauvé, Sébastien

    2012-11-19

    A new solid phase extraction (SPE) method coupled to a high throughput sample analysis technique was developed for the simultaneous determination of nine selected emerging contaminants in wastewater (atrazine, desethylatrazine, 17β-estradiol, ethynylestradiol, norethindrone, caffeine, carbamazepine, diclofenac and sulfamethoxazole). We specifically included pharmaceutical compounds from multiple therapeutic classes, as well as pesticides. Sample pre-concentration and clean-up was performed using a mixed-mode SPE cartridge (Strata ABW) having both cation and anion exchange properties, followed by analysis by laser diode thermal desorption atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS). The LDTD interface is a new high-throughput sample introduction method, which reduces total analysis time to less than 15s per sample as compared to minutes with traditional liquid-chromatography coupled to tandem mass spectrometry (LC-MS/MS). Several SPE parameters were evaluated in order to optimize recovery efficiencies when extracting analytes from wastewater, such as the nature of the stationary phase, the loading flow rate, the extraction pH, the volume and composition of the washing solution and the initial sample volume. The method was successfully applied to real wastewater samples from the primary sedimentation tank of a municipal wastewater treatment plant. Recoveries of target compounds from wastewater ranged from 78% to 106%, the limit of detection ranged from 30 to 122ng L(-1) while the limit of quantification ranged from 90 to 370ng L(-1). Calibration curves in the wastewater matrix showed good linearity (R(2)≥0.991) for all target analytes and the intraday and interday coefficient of variation was below 15%, reflecting a good precision. PMID:23140957

  7. Method development for the determination of 24S-hydroxycholesterol in human plasma without derivatization by high-performance liquid chromatography with tandem mass spectrometry in atmospheric pressure chemical ionization mode.

    Science.gov (United States)

    Sugimoto, Hiroshi; Kakehi, Masaaki; Satomi, Yoshinori; Kamiguchi, Hidenori; Jinno, Fumihiro

    2015-10-01

    We developed a highly sensitive and specific high-performance liquid chromatography with tandem mass spectrometry method with an atmospheric pressure chemical ionization interface to determine 24S-hydroxycholesterol, a major metabolite of cholesterol formed by cytochrome P450 family 46A1, in human plasma without any derivatization step. Phosphate buffered saline including 1% Tween 80 was used as the surrogate matrix for preparation of calibration curves and quality control samples. The saponification process to convert esterified 24S-hydroxycholesterol to free sterols was optimized, followed by liquid-liquid extraction using hexane. Chromatographic separation of 24S-hydroxycholesterol from other isobaric endogenous oxysterols was successfully achieved with gradient mobile phase comprised of 0.1% propionic acid and acetonitrile using L-column2 ODS (2 μm, 2.1 mm id × 150 mm). This assay was capable of determining 24S-hydroxycholesterol in human plasma (200 μL) ranging from 1 to 100 ng/mL with acceptable intra- and inter-day precision and accuracy. The potential risk of in vitro formation of 24S-hydroxycholesterol by oxidation from endogenous cholesterol in human plasma was found to be negligible. The stability of 24S-hydroxycholesterol in relevant solvents and human plasma was confirmed. This method was successfully applied to quantify the plasma concentrations of 24S-hydroxycholesterol in male and female volunteers. PMID:26249017

  8. Negative chemical ionization mass spectrometry

    International Nuclear Information System (INIS)

    This thesis describes some aspects of Negative Chemical Ionization (NCI) mass spectrometry. The reasons for the growing interest in NCI are: (i) to extend the basic knowledge of negative ions and their reactions in the gas phase; (ii) to investigate whether or not this knowledge of negative ions can be used successfully to elucidate the structure of molecules by mass spectrometry. (Auth.)

  9. Chemical protection against ionizing radiation

    Science.gov (United States)

    Maisin, J. R.

    Some of the problems related to chemical protection against ionizing radiation are discussed with emphasis on : definition, classification, degree of protection, mechanisms of action and toxicity. Results on the biological response modifyers (BRMs) and on the combination of nontoxic (i.e. low) doses of sulphydryl radioprotectors and BRMs are presented.

  10. Chemical protection against ionizing radiation

    International Nuclear Information System (INIS)

    Over 40 years have passed since the research of the Manhattan Project suggested the possibility of chemical protection against ionizing radiation. During that time, much has been learned about the nature of radiation-induced injury and the factors governing the expression of that injury. Thousands of compounds have been tested for radioprotective efficacy, and numerous theories have been proposed to account for these actions. The literature on chemical radioprotection is large. In this article, the authors consider several of the mechanisms by which chemicals may protect against radiation injury. They have chosen to accent this view of radioprotector research as opposed to that research geared toward developing specific molecules as protective agents because they feel that such an approach is more beneficial in stimulating research of general applicability. This paper describes the matrix of biological factors upon which an exogenous radioprotector is superimposed, and examines evidence for and against various mechanisms by which these agents may protect biological systems against ionizing radiation. It concludes with a brief outlook for research in chemical radioprotection

  11. Identification of the Related Substances in Ampicillin Capsule by Rapid Resolution Liquid Chromatography Coupled with Electrospray Ionization Tandem Mass Spectrometry

    OpenAIRE

    Lei Zhang; Xian Long Cheng; Yang Liu; Miao Liang; Honghuan Dong; Beiran Lv; Wenning Yang; Zhiqiang Luo; Mingmin Tang

    2014-01-01

    Rapid Resolution Liquid Chromatography coupled with Electrospray Ionization Tandem Mass Spectrometry (RRLC-ESI-MSn) was used to separate and identify related substances in ampicillin capsule. The fragmentation behaviors of related substances were used to identify their chemical structures. Finally, a total of 13 related substances in ampicillin capsule were identified, including four identified components for the first time and three groups of isomers on the basis of the exact mass, fragmenta...

  12. Quantification of hydroxyacetone and glycolaldehyde using chemical ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    K. M. Spencer

    2011-08-01

    Full Text Available Chemical ionization mass spectrometry (CIMS enables online, fast, in situ detection and quantification of hydroxyacetone and glycolaldehyde. Two different CIMS approaches are demonstrated employing the strengths of single quadrupole mass spectrometry and triple quadrupole (tandem mass spectrometry. Both methods are capable of the measurement of hydroxyacetone, an analyte with minimal isobaric interferences. Tandem mass spectrometry provides direct separation of the isobaric compounds glycolaldehyde and acetic acid using distinct, collision-induced dissociation daughter ions. Measurement of hydroxyacetone and glycolaldehyde by these methods was demonstrated during the ARCTAS-CARB 2008 campaign and the BEARPEX 2009 campaign. Enhancement ratios of these compounds in ambient biomass burning plumes are reported for the ARCTAS-CARB campaign. BEARPEX observations are compared to simple photochemical box model predictions of biogenic volatile organic compound oxidation at the site.

  13. Identification of the Related Substances in Ampicillin Capsule by Rapid Resolution Liquid Chromatography Coupled with Electrospray Ionization Tandem Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Lei Zhang

    2014-01-01

    Full Text Available Rapid Resolution Liquid Chromatography coupled with Electrospray Ionization Tandem Mass Spectrometry (RRLC-ESI-MSn was used to separate and identify related substances in ampicillin capsule. The fragmentation behaviors of related substances were used to identify their chemical structures. Finally, a total of 13 related substances in ampicillin capsule were identified, including four identified components for the first time and three groups of isomers on the basis of the exact mass, fragmentation behaviors, retention time, and chemical structures in the literature. This study avoided time-consuming and complex chemosynthesis of related substances of ampicillin and the results could be useful for the quality control of ampicillin capsule to guarantee its safety in clinic. In the meantime, it provided a good example for the rapid identification of chemical structures of related substances of drugs.

  14. Identification of the related substances in ampicillin capsule by rapid resolution liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Zhang, Lei; Cheng, Xian Long; Liu, Yang; Liang, Miao; Dong, Honghuan; Lv, Beiran; Yang, Wenning; Luo, Zhiqiang; Tang, Mingmin

    2014-01-01

    Rapid Resolution Liquid Chromatography coupled with Electrospray Ionization Tandem Mass Spectrometry (RRLC-ESI-MS(n)) was used to separate and identify related substances in ampicillin capsule. The fragmentation behaviors of related substances were used to identify their chemical structures. Finally, a total of 13 related substances in ampicillin capsule were identified, including four identified components for the first time and three groups of isomers on the basis of the exact mass, fragmentation behaviors, retention time, and chemical structures in the literature. This study avoided time-consuming and complex chemosynthesis of related substances of ampicillin and the results could be useful for the quality control of ampicillin capsule to guarantee its safety in clinic. In the meantime, it provided a good example for the rapid identification of chemical structures of related substances of drugs. PMID:25530907

  15. Characterization of Tandem systems of commercial ionization chambers for radiation dosimetry (radiotherapy level)

    CERN Document Server

    Galhardo, E P

    1998-01-01

    The use of X rays for radiotherapy purposes is of great importance for Medicine, and it is necessary to control periodically the performance of the ionization chambers and the radiation beams in order to obtain the best results. The verification of the beam characteristics is made by using standard dosimetry procedures which include the determination of the half-value layers and the exposure rates or the absorbed dose rates in air. Several Tandem systems were set up and tested, using commercial ionization chambers in the energy interval from 14 up to 130 KeV at the Instrumentation Calibration Laboratory of IPEN and at other three institutions, in substitution to the routine conventional procedure of determination of half-value layers using absorbers. The obtained results show the usefulness of these Tandem system for the routine dosimetric procedures of radiotherapy X radiation beams.

  16. High explosives vapor detection by atmospheric sampling glow discharge ionization/tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    McLuckey, S.A.; Goeringer, D.E.; Asano, K.G. [Oak Ridge National Lab., TN (United States). Chemical and Analytical Sciences Div.

    1996-02-01

    The combination of atmospheric sampling glow discharge ionization with tandem mass spectrometry for the detection of traces of high explosives is described. Particular emphasis is placed on use of the quadrupole ion trap as the type of tandem mass spectrometer. Atmospheric sampling glow discharge provides a simple, rugged, and efficient means for anion formation while the quadrupole ion trap provides for efficient tandem mass spectrometry. Mass selective ion accumulation and non-specific ion activation methods can be used to overcome deleterious effects arising from ion/ion interactions. Such interactions constitute the major potential technical barrier to the use of the ion trap for real-time monitoring of targeted compounds in uncontrolled and highly variable matrices. Tailored waveforms can be used to effect both mass selective ion accumulation and ion activation. Concatenated tailored waveforms allow for both functions in a single experiment thereby providing the capability for monitoring several targeted species simultaneously. The combination of atmospheric sampling glow discharge ionization with a state-of-the-art analytical quadrupole ion trap is a highly sensitive and specific detector for traces of high explosives. The combination is also small and inexpensive relative to virtually any other form of tandem mass spectrometry. The science and technology underlying the glow discharge/ion trap combination is sufficiently mature to form the basis for an engineering effort to make the detector portable. 85 refs.

  17. Chemical protection against ionizing radiation. Final report

    International Nuclear Information System (INIS)

    The scientific literature on radiation-protective drugs is reviewed. Emphasis is placed on the mechanisms involved in determining the sensitivity of biological material to ionizing radiation and mechanisms of chemical radioprotection. In Section I, the types of radiation are described and the effects of ionizing radiation on biological systems are reviewed. The effects of ionizing radiation are briefly contrasted with the effects of non-ionizing radiation. Section II reviews the contributions of various natural factors which influence the inherent radiosensitivity of biological systems. Inlcuded in the list of these factors are water, oxygen, thiols, vitamins and antioxidants. Brief attention is given to the model describing competition between oxygen and natural radioprotective substances (principally, thiols) in determining the net cellular radiosensitivity. Several theories of the mechanism(s) of action of radioprotective drugs are described in Section III. These mechanisms include the production of hypoxia, detoxication of radiochemical reactive species, stabilization of the radiobiological target and the enhancement of damage repair processes. Section IV describes the current strategies for the treatment of radiation injury. Likely areas in which fruitful research might be performed are described in Section V. 495 references

  18. Chemical protection against ionizing radiation. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Livesey, J.C.; Reed, D.J.; Adamson, L.F.

    1984-08-01

    The scientific literature on radiation-protective drugs is reviewed. Emphasis is placed on the mechanisms involved in determining the sensitivity of biological material to ionizing radiation and mechanisms of chemical radioprotection. In Section I, the types of radiation are described and the effects of ionizing radiation on biological systems are reviewed. The effects of ionizing radiation are briefly contrasted with the effects of non-ionizing radiation. Section II reviews the contributions of various natural factors which influence the inherent radiosensitivity of biological systems. Inlcuded in the list of these factors are water, oxygen, thiols, vitamins and antioxidants. Brief attention is given to the model describing competition between oxygen and natural radioprotective substances (principally, thiols) in determining the net cellular radiosensitivity. Several theories of the mechanism(s) of action of radioprotective drugs are described in Section III. These mechanisms include the production of hypoxia, detoxication of radiochemical reactive species, stabilization of the radiobiological target and the enhancement of damage repair processes. Section IV describes the current strategies for the treatment of radiation injury. Likely areas in which fruitful research might be performed are described in Section V. 495 references.

  19. Application of a tandem ionization chamber in a quality control program of X-ray beams, radiotherapy level

    International Nuclear Information System (INIS)

    A tandem ionization chamber, developed at the Instituto de Pesquisas Energeticas e Nucleares (IPEN), for X radiation beams, radiotherapy level, was applied into a quality control program of the Calibration Laboratory of IPEN. This ionization chamber is composed by two ionization chambers, with a volume of 0.6 cm3 each one. Its inner plane-parallel electrodes and guard rings are made of different materials: one is made of aluminum and the other is made of graphite. Because of this difference in materials, the ionization chamber forms a tandem system. The relative response of the calibration factors of both sides of the chamber allows an easy verification of the X-ray beam qualities stability. The ionization chamber was submitted to some tests to verify the stability of its response: leakage current before and after exposure, repeatability and reproducibility. The performance of the ionization chamber was satisfactory. (author)

  20. Analysis of Norditerpenoid Alkaloids Extracted from Aconitum sinomantanum Nakai by Electrospray Ionization Tandem Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Electrospray ionization mass spectrometry(ESI-MS) was applied simultaneously in determining norditerpenoid alkaloids from the roots of Aconitum sinomantanum Nakai (RAS) based on molecular mass information. The tandem mass spectra(ESI-MSn) provided the alkaloidal structural information, through which the existence of these alkaloids was further confirmed. Accordingly, six known norditerpenoid alkaloids were simultaneously determined on the basis of their ESI-MSn spectra. Furthermore, based on the diagnostic fragmentation pathways of alkaloidal MSn, a rapid method for direct detection and characterization of alkaloids from an ethanolic extract of RAS was described.

  1. Electrospray-assisted laser desorption/ionization and tandem mass spectrometry of peptides and proteins.

    Science.gov (United States)

    Peng, Ivory X; Shiea, Jentaie; Ogorzalek Loo, Rachel R; Loo, Joseph A

    2007-01-01

    We have constructed an electrospray-assisted laser desorption/ionization (ELDI) source which utilizes a nitrogen laser pulse to desorb intact molecules from matrix-containing sample solution droplets, followed by electrospray ionization (ESI) post-ionization. The ELDI source is coupled to a quadrupole ion trap mass spectrometer and allows sampling under ambient conditions. Preliminary data showed that ELDI produces ESI-like multiply charged peptides and proteins up to 29 kDa carbonic anhydrase and 66 kDa bovine albumin from single-protein solutions, as well as from complex digest mixtures. The generated multiply charged polypeptides enable efficient tandem mass spectrometric (MS/MS)-based peptide sequencing. ELDI-MS/MS of protein digests and small intact proteins was performed both by collisionally activated dissociation (CAD) and by nozzle-skimmer dissociation (NSD). ELDI-MS/MS may be a useful tool for protein sequencing analysis and top-down proteomics study, and may complement matrix-assisted laser desorption/ionization (MALDI)-based measurements. PMID:17639579

  2. Analysis of alcohols, as dimethylglycine esters, by electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Johnson, D W

    2001-03-01

    Dimethylglycine (DMG) esters are new derivatives for the rapid, sensitive and selective analysis of primary and secondary alcohols, in complex mixtures, by electrospray ionization tandem mass spectrometry (ESI-MS/MS). Their development was inspired by the use of the complementary dimethylaminoethyl esters for the trace, rapid analysis of fatty acids. DMG esters are simply prepared by heating a dichloromethane solution of the imidazolide of dimethylglycine, containing triethylamine, and an alcohol. DMG esters of long-chain fatty alcohols, isoprenoidal alcohols and hydroxy-acids are analysed by electrospray ionization tandem mass spectrometry with a precursor ion of m/z 104 scan. Diols, glyceryl esters, glyceryl ethers and some sterols are analysed by a neutral loss of 103 Da scan. Trimethylglycine (TMG) ester iodides, prepared by alkylation of DMG esters with methyl iodide, are more sensitive derivatives for molecules containing secondary alcohol groups, such as cholesterol and gibberellic acid. They are analysed by a precursor ion of m/z 118 scan. DMG or TMG derivatives were shown to be at least comparable and sometimes an order of magnitude more sensitive than N-methylpyridyl ether derivatives for ESI-MS/MS analysis of the different classes of alcohols. Applications of these derivatives for the diagnosis of inherited disorders and the analysis of natural products are presented. PMID:11312519

  3. Nontarget analysis of urine by electrospray ionization-high field asymmetric waveform ion mobility-tandem mass spectrometry.

    Science.gov (United States)

    Beach, Daniel G; Gabryelski, Wojciech

    2011-12-01

    Nearly a decade after first commercialization, high field asymmetric waveform ion mobility spectrometry (FAIMS) has yet to find its place in routine chemical analysis. Prototypes have been used to demonstrate the utility of this separation technique combined with mass spectrometry (MS). Unfortunately, first generation commercial FAIMS instruments have gone practically unused by early adopters. Here, we show this to be due to poor ion transmission in the FAIMS-MS source interface. We present simple instrumental modifications and optimization of experimental conditions to achieve good performance from the first generation commercial FAIMS device (the Ionalytics Selectra) coupled to a high resolution Q-TOF-MS. In combination with nanospray ionization, we demonstrate for the first time the nontarget analysis of urine by FAIMS with minimal sample preparation. We show the unique suitability of electrospray ionization (ESI)-FAIMS-MS for identification of low abundance species such as urinary biomarkers of damage of nucleic acids in a complex biological matrix. The elimination of electrospray noise and matrix components by FAIMS and the continuous flow of analytes through FAIMS for accurate and tandem mass analysis produce high quality spectral data suitable for structural identification of unknowns. These characteristics make ESI-FAIMS-MS ideal for nontarget identification, even when compared to high efficiency LC-ESI-MS. PMID:21978137

  4. TANDEM

    Data.gov (United States)

    Federal Laboratory Consortium — The Tandem Van de Graaff facility provides researchers with beams of more than 40 different types of ions - atoms that have been stripped of their electrons. One of...

  5. Characteristic Fragmentation Behavior of Steroidal Phosphoramidate Conjugates in Electrospray Ionization Tandem Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    JI, San-Hao; JU, Yong; XIAO, Qiang; ZHAO, Yu-Fen

    2006-01-01

    Novel steroidal phosphoramidate conjugates of 3'-azido-2',3'-dideoxythymidine (AZT) and amino acid esters were synthesized and determined by positive and negative ion electrospray ionization mass spectrometry. The MS fragmentation behaviors of the steroidal phosphoramidate conjugates have been investigated in conjunction with tandem mass spectrometry of ESI-MS/MS. There were three characteristic fragment ions in the positive ion ESI mass spectra, which were the Na adduct ions with loss of steroidal moiety, amino acid ester moiety from pseudo molecular ion (M+Na)+, and the phosphoamino acid methyl ester Na adduct ion by a-cleavage of the phosphoramidate respectively. The main fragment ions in negative ion ESI mass spectra were the ion (M-HN3)-, the ion (M - AZT - H)- , and the ion (M-steroidal moiety-H)- besides the pseudo molecular ion (M-H)-. The fragmentation patterns did not depend on the attached amino acid ester moiety.

  6. Characterization of Proanthocyanidins from Parkia biglobosa (Jacq. G. Don. (Fabaceae by Flow Injection Analysis — Electrospray Ionization Ion Trap Tandem Mass Spectrometry and Liquid Chromatography/Electrospray Ionization Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Wagner Vilegas

    2013-03-01

    Full Text Available The present study investigates the chemical composition of the African plant Parkia biglobosa (Fabaceae roots and barks by Liquid Chromatography - Electrospray Ionization and Direct Injection Tandem Mass Spectrometry analysis. Mass spectral data indicated that B-type oligomers are present, namely procyanidins and prodelphinidins, with their gallate and glucuronide derivatives, some of them in different isomeric forms. The analysis evidenced the presence of up to 40 proanthocyanidins, some of which are reported for the first time. In this study, the antiradical activity of extracts of roots and barks from Parkia biglobosa was evaluated using DPPH method and they showed satisfactory activities.

  7. Chemical protection against ionizing radiation: a survey of possible mechanisms

    International Nuclear Information System (INIS)

    A comparative survey is given of the hypotheses which have been proposed to explain the protecting and sensitizing action of chemical substances towards ionizing radiation such as gamma radiation or x radiation

  8. Comprehensive metabolite profiling of Plantaginis Semen using ultra high performance liquid chromatography with electrospray ionization quadrupole time-of-flight tandem mass spectrometry coupled with elevated energy technique.

    Science.gov (United States)

    Wang, Dandan; Qi, Meng; Yang, Qiming; Tong, Renchao; Wang, Rui; Bligh, S W Annie; Yang, Li; Wang, Zhengtao

    2016-05-01

    Plantaginis Semen is commonly used in traditional medicine to treat edema, hypertension, and diabetes. The commercially available Plantaginis Semen in China mainly comes from three species. To clarify the chemical composition and distinct different species of Plantaginis Semen, we established a metabolite profiling method based on ultra high performance liquid chromatography with electrospray ionization quadrupole time-of-flight tandem mass spectrometry coupled with elevated energy technique. A total of 108 compounds, including phenylethanoid glycosides, flavonoids, guanidine derivatives, terpenoids, organic acids, and fatty acids, were identified from Plantago asiatica L., P. depressa Willd., and P. major L. Results showed significant differences in chemical components among the three species, particularly flavonoids. This study is the first to provide a comprehensive chemical profile of Plantaginis Semen, which could be involved into the quality control, medication guide, and developing new drug of Plantago seeds. PMID:27030316

  9. Phosphopeptide detection and sequencing by matrix-assisted laser desorption/ionization quadrupole time-of-flight tandem mass spectrometry

    DEFF Research Database (Denmark)

    Bennett, Keiryn L; Stensballe, Allan; Podtelejnikov, Alexandre V;

    2002-01-01

    localization of one, three or four phosphorylated amino acid residues in phosphopeptides up to 3.1 kDa. Tandem mass spectra of two different phosphotyrosine peptides permitted amino acid sequence determination and localization of one and three phosphorylation sites, respectively. The phosphotyrosine immonium...... ion at m/z 216.04 was observed in these MALDI low-energy CID tandem mass spectra. Elimination of phosphate groups was evident from the triphosphorylated peptide but not from the monophosphorylated species. The main fragmentation pathway for the synthetic phosphothreonine-containing peptide and for......A prototype matrix-assisted laser desorption/ionization quadrupole time-of-flight (MALDI-TOF) tandem mass spectrometer was used to sequence a series of phosphotyrosine-, phosphothreonine- and phosphoserine-containing peptides. The high mass resolution and mass accuracy of the instrument allowed the...

  10. Glycerophospholipid analysis of Eastern red bat (Lasiurus borealis) hair by electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Pannkuk, Evan L; McGuire, Liam P; Gilmore, David F; Savary, Brett J; Risch, Thomas S

    2014-03-01

    Pilosebaceous units found in the mammalian integument are composed of a hair follicle, the proximal portion of the hair shaft, a sebaceous gland, and the erector pili muscle. Pilosebaceous units release protective oils, or sebum, by holocrine secretion onto skin and hair through rupturing of sebocytes. Sebum is composed largely of polar and neutral lipids including glycerolipids, free fatty acids, sterols, wax esters, sterol esters, and squalene. In addition to these lipid classes, there is a small proportion of ionic/anionic glycerophospholipids (GPs). Composition of GPs on hair is rarely addressed despite their broad biological activities as signaling molecules and membrane stability. Furthermore, knowledge on GP composition in bats is lacking. Bat GP composition is important to document due to GP roles ranging from decreasing drag during migration to interaction with the integumentary microbiome. In this study, we analyzed GP molecular composition with liquid chromatography electrospray ionization tandem mass spectrometry and compared GP content to previous literature. A total of 152 GPs were detected. Broad GP classes identified include lysophosphatidylcholine, phosphatidylcholine (PC), lysophosphatidylethanolamine, phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, phosphatidic acid, and phosphatidylglycerol, with PC being the most abundant class. The acyl components were consistent with fatty acid methyl esters and triacylglyceride moieties found in Eastern red bat sebum. Glycerophospholipid proportions of the hair surface were different from a previous study on bat lung surfactants. This study determined the broad class and molecular species of bat sebum GPs that may be used in future ecological studies in vespertilionid bats. PMID:24532214

  11. Identification of forced degradation products of tamsulosin using liquid chromatography/electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Namdev, Deepak; Borkar, Roshan M; Raju, B; Kalariya, Pradipbhai D; Rahangdale, Vinodkumar T; Gananadhamu, S; Srinivas, R

    2014-01-01

    A rapid and gradient high-performance liquid chromatography combined with quadrupole time-of-flight electrospray ionization tandem mass spectrometry (LC/Q-TOF-ESI-MS/MS) method has been developed for the identification and structural characterization of stressed degradation products of tamsulosin. Tamsulosin, a selective α1-adrenoceptor antagonist, was subjected to forced degradation studies under hydrolytic (acid, base and neutral), oxidative, photolytic and thermal stress conditions as per ICH guidelines Q1A (R2). The drug degraded significantly under hydrolytic (base and neutral), thermal, oxidative and photolytic conditions, while it was stable to acid hydrolytic stress conditions. A total of twelve degradation products were formed and the chromatographic separation of the drug and its degradation products were achieved on a GRACE C-18 column (250mm×4.6mm, 5μm). All the degradants have been identified and characterized by LC/ESI-MS/MS and accurate mass measurements. To elucidate the structures of degradation products, fragmentation of the [M+H](+) ions of tamsulosin and its degradation products was studied by using LC-MS/MS experiments combined with accurate mass measurements. The product ions of all the protonated degradation products were compared with the product ions of protonated tamsulosin to assign most probable structures for the observed degradation products. PMID:24083958

  12. A method for profiling gangliosides in animal tissues using electrospray ionization-tandem mass spectrometry.

    Science.gov (United States)

    Tsui, Zhao-Chun; Chen, Qi-Rui; Thomas, Michael J; Samuel, Michael; Cui, Zheng

    2005-06-15

    Gangliosides are critical in many functions of mammalian cells but present as a minor lipid component with many molecular species of subtle differences. Conventional strategies for profiling gangliosides suffer from poor reproducibility, low sensitivity, and low-throughput capacity. Prior separation of gangliosides by thin-layer chromatography and/or high-performance liquid chromatography not only was laborious and tedious but also could introduce uneven losses of molecular species. We developed a new strategy of using electrospray ionization-tandem mass spectrometry (ESI-MS/MS) to profile gangliosides with high-throughput potential. This strategy involves three new findings: (i) collision-induced fragmentation of gangliosides gave rise to a common ion of m/z 290, a derivative of N-acetylneuraminic acid; (ii) phospholipids exert a profound suppression of ganglioside detection in ESI-MS/MS to prevent a direct detection in total cellular lipid extracts; and (iii) enrichment of gangliosides in the aqueous phase from total cellular lipid extracts eliminates the damping effect of phospholipids and permits direct precursor scan. PMID:15907870

  13. Application of gas chromatography–(triple quadrupole) massspectrometry with atmospheric pressure chemical ionization for thedetermination of multiclass pesticides in fruits and vegetables

    NARCIS (Netherlands)

    Cherta, L.; Portoles, T.; Beltran, J.; Pitarch, E.; Mol, J.G.J.; Hernandez, F.

    2013-01-01

    A multi-residue method for the determination of 142 pesticide residues in fruits and vegetables has been developed using a new atmospheric pressure chemical ionization (APCI) source for coupling gas chromatography (GC) to tandem mass spectrometry (MS). Selected reaction monitoring (SRM) mode has bee

  14. Chemical effects of ionizing radiation and sonic energy in the context of chemical evolution

    International Nuclear Information System (INIS)

    Ionizing radiation and sonic energy are considered as sources for chemical evolution processes. These sources have still a modest place in the interdisciplinary approach for the prebiological synthesis of organic compounds. Studies in Radiation Chemistry and Sonochemistry can provide a deeper insight into the chemical processes that may have importance for prebiotic chemistry. The present work concerns the analysis of some chemical reactions induced by ionizing radiation or cavitation in aqueous media that may be relevant to chemical evolution studies. (author)

  15. Mass spectrometry analysis of polychlorinated biphenyls: chemical ionization and selected ion chemical ionization using methane as a reagent gas

    OpenAIRE

    RAYMOND E. MARCH; MILA D. LAUSEVIC; TATJANA M. VASILJEVIC

    2000-01-01

    In the present paper a quadrupole ion trap mass spectrometer, coupled with a gas chromatograph, was used to compare the electron impact ionization (EI) and chemical ionization (Cl) technique, in terms of their selectivity in polychlorinated biphenyls (PCBs) quantitative analysis. The experiments were carried out with a modified Varian SATURN III quadrupole ion-storage mass spectrometer equipped with Varian waveform generator, coupled with a gas chromatograph with DB-5 capillary column. The di...

  16. State and tendencies of chemical protection against ionizing radiation

    International Nuclear Information System (INIS)

    Papers published in 1976 in the field of chemical protection against ionizing radiation are reviewed. Protection studies in vitro and in vivo, the biochemical, pharmacological and toxic effects, the mechanisms of protection of radioprotective agents and the trends in this field of research are described. (author)

  17. State and tendencies of chemical protection against ionizing radiation

    International Nuclear Information System (INIS)

    Papers published in 1979 and 1980 in the field of chemical protection against ionizing radiation are reviewed. Protection studies in in-vivo and model systems, the biochemical, pharmacological and toxic effects, and modes of action of radioprotective agents are described and the trends in this field of research estimated. (author)

  18. State and tendencies of chemical protection against ionizing radiation

    International Nuclear Information System (INIS)

    Papers published in 1975 in the field of chemical protection against ionizing radiation are reviewed. Protection studies in vitro and in vivo, the biochemical, pharmacological and toxic effects, the mechanisms of protection of radioprotective agents and the trends in this field of research are described. (author)

  19. State and tendencies of chemical protection against ionizing radiation

    International Nuclear Information System (INIS)

    Papers published in 1978 in the field of chemical protection against ionizing radiation are reviewed. Protection studies in in-vivo and model systems, the biochemical, pharmacological and toxic effects, and modes of action of radioprotective agents are described and the trends in this field of research appreciated. (author)

  20. State and tendencies of chemical protection against ionizing radiation

    International Nuclear Information System (INIS)

    Papers published in 1974 in the field of chemical protection against ionizing radiation are reviewed. Protection studies in vitro and in vivo, the biochemical, pharmacological and toxic effects, the mechanisms of protection of radioprotective agents and the trends in this field of research are described. (author)

  1. Hydrocarbon analysis using desorption atmospheric pressure chemical ionization

    KAUST Repository

    Jjunju, Fred P M

    2013-07-01

    Characterization of the various petroleum constituents (hydronaphthalenes, thiophenes, alkyl substituted benzenes, pyridines, fluorenes, and polycyclic aromatic hydrocarbons) was achieved under ambient conditions without sample preparation by desorption atmospheric pressure chemical ionization (DAPCI). Conditions were chosen for the DAPCI experiments to control whether ionization was by proton or electron transfer. The protonated molecule [M+H]+ and the hydride abstracted [MH]+ form were observed when using an inert gas, typically nitrogen, to direct a lightly ionized plasma generated by corona discharge onto the sample surface in air. The abundant water cluster ions generated in this experiment react with condensed-phase functionalized hydrocarbon model compounds and their mixtures at or near the sample surface. On the other hand, when naphthalene was doped into the DAPCI gas stream, its radical cation served as a charge exchange reagent, yielding molecular radical cations (M+) of the hydrocarbons. This mode of sample ionization provided mass spectra with better signal/noise ratios and without unwanted side-products. It also extended the applicability of DAPCI to petroleum constituents which could not be analyzed through proton transfer (e.g., higher molecular PAHs such as chrysene). The thermochemistry governing the individual ionization processes is discussed and a desorption/ionization mechanism is inferred. © 2012 Elsevier B.V.

  2. Metabolism of halogenated compounds in the white rot fungus Bjerkandera adusta studied by membrane inlet mass spectrometry and tandem mass spectrometry

    DEFF Research Database (Denmark)

    Beck, Hans Christian; Lauritsen, F.R.; Patrick, J.S.;

    1996-01-01

    Membrane inlet mass spectrometry has been used for the characterization of halogenated organic compounds produced by the fungus Bjerkandera adusta. Using this technique, electron impact-, chemical ionization-, electron capture negative chemical ionization-mass spectra and tandem mass spectra were...

  3. Gasification and Ionization of Chemically Complex Liquids for FRC Injection

    Science.gov (United States)

    Holmes, Michael; Hill, Carrie

    2014-10-01

    Ion thrusters provide reliable and efficient spacecraft propulsion but are limited to noble gas propellants to limit chemical attack of components. However, thrusters based on Field Reversed Configuration (FRC) plasmas are becoming a reality. High beta compact-toroids are generated within an FRC thruster and then expelled to provide thrust. The closed field lines restrict the plasma from attacking thruster components. More convenient propellants such as water are therefore possible. The FRC thruster would generate a series of compact-toroids (plasmoids) to develop continuous spacecraft thrust. Each plasmoid ejection would empty the discharge region. The feed system would then refill the discharge region with partially ionized gas for the next discharge. The ionization part of this feed system is the subject of this paper. The question is how to produce a uniform, chemically complex, ionized gas within the discharge region that optimizes compact-toroid formation? We will be measuring chemical state, ionization state, and uniformity as the propellant enters the discharge region.

  4. Elucidation of O-Phosphoryl and N-Phosphoryl Amino Acids by Electrospray Ionization Tandem Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Jian-Chen(张建臣); CAO,Shu-Xiaa(曹书霞); XU,Juna(徐军); LIAO,Xin-Cheng(廖新成); ZHAO,Yu-Fen(赵玉芬)

    2004-01-01

    Mass spectroscopic characteristics of phosphoryl amino acids were studied in detail by positive and negative electrospray ionization mass spectrometry (ESI-MS) in conjunction with tandem mass spectrometry (MS/MS). Besides N-diisopropyloxyphosphoryl amino acids (N-DIPP-AA), O-phospho- and O-diisopropyloxyphosphoryl amino acids (O-DIPP-AA) were studied and compared to N-DIPP-AA. The fragmentation pathways of [M+H]+, [M+Na]+ and [M-H]- ions of phosphoryl amino acids were summarized. In addition to several similar patterns,each of them showed its characteristic fragmention.

  5. Characterization of gallotannins from Astronium species by flow injection analysis- electrospray ionization-ion trap-tandem mass spectrometry and matrix-assisted laser desorption/ionization time-of- flight mass spectrometry.

    Science.gov (United States)

    da Silva, Viviane Cândida; Napolitano, Assunta; Eletto, Daniela; Rodrigues, Clenilson Martins; Pizza, Cosimo; Vilegas, Wagner

    2011-01-01

    The species Astronium urundeuva (Allemao) Engl. and Astronium graveolens Jacq., which are used in Brazilian folk medicine to treat allergies, inflammation, diarrhea and ulcers, were investigated for their composition. The aim of this study was to define a rapid and reliable analytical approach, based on the flow-injection analysis-electrospray ionization-ion trap-tandem mass spectrometry (FIA-ESI-IT-MS-MS) and matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry (MALDI-ToF-MS), to investigate the full range of hydrolyzable tannins present in the extracts of these Astronium species. The MALDI-ToF-MS analysis allowed us to ascertain the presence of hydrolysable tannins in both Astronium species as a series of gallotannins with degrees of polymerization of 7 to 13 galloyl units. Moreover, the analysis by FIA-ESI-IT-MS-MS, as well as confirming this result and chemically defining gallotannins as galloylglucose compounds, highlighted the presence of further classes of hydrolysable tannins, such as hexahydrodiphenoyl esters of glucose and some gallic acid derivatives, providing information about their structure by a careful study of their fragmentation patterns. Finally, the evaluation of the number of positional isomers of gallotannins occurring in both Astronium species was obtained by high-performance liquid chromatography-electrospray ionization-ion trap mass spectrometry (HPLC/ESI-IT-MS). This is the first mass spectrometric evidence relating to the existence of gallotannins in Astronium genus. PMID:22006629

  6. Conversion of 3-nitrotyrosine to 3-aminotyrosine residues facilitates mapping of tyrosine nitration in proteins by electrospray ionization-tandem mass spectrometry using electron capture dissociation.

    Science.gov (United States)

    Guo, Jia; Prokai, Laszlo

    2012-12-01

    Protein tyrosine nitration is associated with oxidative stress and various human diseases. Tandem mass spectrometry has been the method of choice for the identification and localization of this posttranslational modification to understand the underlying mechanisms and functional consequences. Due to the electron predator effect of the nitro group limiting fragmentation of the peptide backbone, electron-based dissociation has not been applicable, however, to nitrotyrosine-containing peptides. A straightforward conversion of the nitrotyrosine to the aminotyrosine residues is introduced to address this limitation. When tested with nitrated ubiquitin and human serum albumin as model proteins in top-down and bottom-up approaches, respectively, this chemical derivatization enhanced backbone fragmentation of the corresponding nitroproteins and nitropeptides by electron capture dissociation (ECD). Increased sequence coverage has been obtained by combining in the bottom-up strategy the conversion of nitrotyrosine to aminotyrosine and introducing, in addition to trypsin, a further digesting enzyme of complementary specificity, when protein nitration was mapped by liquid chromatography-electrospray ionization tandem mass spectrometry using both collision-induced dissociation (CID) and ECD. PMID:23280749

  7. Study of electrospray ionization tandem mass spectrometry of the benzofuranone compounds

    Institute of Scientific and Technical Information of China (English)

    Zhan Qi Niu; Yu Min Sun; Feng Niu; Jian Han; Da Wei Chen

    2008-01-01

    A detailed analysis of benzofuranone compounds under multiple tandem mass spectrometry (ESI-MS(n)) conditions is reported. Element composition data of the fragment ions were obtained with the aid of comparison of the multiple tandem mass spectra of four compounds, and the structures of which are identical except for some substituted groups or epimers or ra-r/ww-isomers. Attempts have been made to provide rational pathways for the formation of the fragment ions from these protonated compounds. And the structure-fragmentation relationships will facilitate the characterization of the structures of other analogs.

  8. Characterization of nonpolar lipids and steroids by using laser-induced acoustic desorption/chemical ionization, atmospheric pressure chemical ionization, and electrospray ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Z; Daiya, S; Kenttämaa, Hilkka I

    Laser-induced acoustic desorption (LIAD) combined with ClMn(H{sub 2}O){sup +} chemical ionization (CI) was tested for the analysis of nonpolar lipids and selected steroids in a Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR). The nonpolar lipids studied, cholesterol, 5α-cholestane, cholesta-3,5-diene, squalene, and β-carotene, were found to solely form the desired water replacement product (adduct-H{sub 2}O) upon reaction with the ClMn(H{sub 2}O){sup +} ions. The steroids, androsterone, dehydroepiandrosterone (DHEA), estrone, estradiol, and estriol, also form abundant adduct-H{sub 2}O ions, but less abundant adduct-2H{sub 2}O ions were also observed. Neither (+)APCI nor (+)ESI can ionize the saturated hydrocarbon lipid, cholestane. APCI successfully ionizes the unsaturated hydrocarbon lipids to form exclusively the intact protonated analytes. However, it causes extensive fragmentation for cholesterol and the steroids. The worst case is cholesterol that does not produce any stable protonated molecules. On the other hand, ESI cannot ionize any of the hydrocarbon analytes, saturated or unsaturated. However, ESI can be used to protonate the oxygen-containing analytes with substantially less fragmentation than for APCI in all cases except for cholesterol and estrone. In conclusion, LIAD/ClMn(H{sub 2}O){sup +} chemical ionization is superior over APCI and ESI for the mass spectrometric characterization of underivatized nonpolar lipids and steroids.

  9. Specific determination of 20 primary aromatic amines in aqueous food simulants by liquid chromatography-electrospray ionization-tandem mass spectrometry

    DEFF Research Database (Denmark)

    Mortensen, Sarah Kelly; Trier, Xenia Thorsager; Foverskov, Annie;

    2005-01-01

    A multi-analyte method without any pre-treatment steps using reversed-phase liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) was developed and applied for the determination of 20 primary aromatic amines (PAA) associated with polyurethane (PUR) products or azo...

  10. Identification of glyceollin metabolites derived from conjugation with glutathione and glucuronic acid in rats by on-line liquid chromatography-electrospray ionization tandem mass spectrometry

    Science.gov (United States)

    Glyceollin-related metabolites produced in rats following oral glyceollin administration were screened and identified by precursor and product ion scanning using liquid chromatography, coupled on-line with electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS), to identify all glyceollin me...

  11. Detection and Characterization of Non-covalent Complex between Lappaconitine and β-Cyclodextrin by Electrospray Ionization Tandem Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    Qing Xuan XU; Li LI; Hao YUE; Zhi Qiang LIU; Ming Quan GUO; Shu Ying LIU

    2006-01-01

    The non-covalent complexes between lappaconitine (LA) and β-cyclodextrin (β-CD) have been detected and characterized by electrospray ionization combined with ion trap tandem mass spectrometry (ESI-MSn). The experimental results showed that only 1:1 non-covalent complex can be formed in different starting molar ratios of LA to β-CD. Furthermore, the diagnostic fragmentation of the β-CD-LA complex, with a significant contribution of covalent fragmentation of LA leaving the N-acetyl anthranoyl (AN) moiety inserted to β-CD, provided the convincing evidence for the formation of non-covalent complex between LA and β-CD and the cite of LA molecule included to cavity of β-CD assigned to AN residue.

  12. Rapid separation and identification of multiple constituents in Danhong Injection by ultra-high performance liquid chromatography coupled to electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

    Science.gov (United States)

    Zhang, Qun-Qun; Dong, Xin; Liu, Xin-Guang; Gao, Wen; Li, Ping; Yang, Hua

    2016-02-01

    To characterize and identify multiple constituents in Danhong injection (DHI), a fast ultra-high performance liquid chromatography coupled to electrospray ionization quadrupole time-of-flight tandem mass spectrometry (UHPLC-ESI-QTOF/MS) method was established and validated in the present study. A total of 63 compounds, including 33 phenolic acids, 2 C-glycosyl quinochalcones, 6 flavonoid O-glycosides, 4 iridoid glycosides, 6 organic acids, 5 amino acids, and 3 nucleosides, were identified or tentatively characterized. In conclusion, the UHPLC-ESI-QTOF/MS method is useful and efficient for in-depth structural elucidation of chemical compounds in complex matrices of herbal medicines such as DHI. PMID:26968681

  13. Chemical protection and sensitization to ionizing radiation:molecular investigations

    International Nuclear Information System (INIS)

    Chemical radioprotection and radiosensitization are induced by the presence of certain chemical compounds, which reduce or enhance the effect of ionizing radiation on living organisms. Such substances are either naturally present or may be artificially introduced in the living cells. Chemical radioprotectors are interesting for possible application in the health protection of both professionally exposed workers and patients treated by radiation for diagnostic and thereapeutic purposes. Interest in chemical radiosensitization has increased recently because of its potential application in the radiotherapy of tumours. Both radioprotection and radiosensitization occur by means of complicated mechanisms, which at first correspond to very fast reactions. The mechanism of the interaction between such substances and radiation-induced biological radicals has been investigated by means of pulse radiolysis and rapid mixing techniques. Examples of the application of these techniques are given to illustrate how information has been obtained on the molecular basis of radiation chemical modi-fication at the cellular level. In particular some interactions between model systems of biological interest (DNA, DNA components, enzymes, amino acids, etc.) and sulphur-containing radioprotectors (glutathione, cysteine, etc.) and/or electroaffinic radiosensitizers, are described. (H.K.)

  14. Mechanism of Interaction between Ionizing Radiation and Chemicals

    International Nuclear Information System (INIS)

    This research project has been carried out jointly with INP (Poland) to develop technologies for 'Mechanism of Interaction between ionizing radiation and chemicals. Several biological end-points were assessed in experimental organisms such as higher plants, rats, cell lines and yeast cells to establish proper bioassay techniques. The Tradescantia somatic cell mutation assay was carried out, and immunohistochemistry and hormone assays were done in Fisher 344 rats and cell lines to analyse the combined effect of ionizing radiation with mercury chloride. Using the common regularities of combined actions of two factors, a theoretical model was established, and applied to the thermo radiation action and synergism between two chemicals, as well. The model approach made it possible to predict the condition under which the maximum synergism could be attained. The research results were published in high standard journals and presented in the scientific conferences to verify KAERI's current technology level. The experience of collaboration can be used as a fundamental tool for multinational collaboration, and make the role of improving relationship between Korea and Poland

  15. Mechanism of Interaction between Ionizing Radiation and Chemicals

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jin Kyu; Lee, B. H.; Shin, H. S. (and others)

    2008-03-15

    This research project has been carried out jointly with INP (Poland) to develop technologies for 'Mechanism of Interaction between ionizing radiation and chemicals{sup .} Several biological end-points were assessed in experimental organisms such as higher plants, rats, cell lines and yeast cells to establish proper bioassay techniques. The Tradescantia somatic cell mutation assay was carried out, and immunohistochemistry and hormone assays were done in Fisher 344 rats and cell lines to analyse the combined effect of ionizing radiation with mercury chloride. Using the common regularities of combined actions of two factors, a theoretical model was established, and applied to the thermo radiation action and synergism between two chemicals, as well. The model approach made it possible to predict the condition under which the maximum synergism could be attained. The research results were published in high standard journals and presented in the scientific conferences to verify KAERI's current technology level. The experience of collaboration can be used as a fundamental tool for multinational collaboration, and make the role of improving relationship between Korea and Poland.

  16. A new multiplex method for the diagnosis of peroxisomal disorders allowing simultaneous determination of plasma very-long-chain fatty acids, phytanic, pristanic, docosahexaenoic and bile acids by high-performance liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    Science.gov (United States)

    Semeraro, Michela; Rizzo, Cristiano; Boenzi, Sara; Cappa, Marco; Bertini, Enrico; Antonetti, Giacomo; Dionisi-Vici, Carlo

    2016-07-01

    Peroxisomal disorders (PDs) present with wide phenotypic variability. An appropriate diagnosis requires a complete analysis of peroxisomal metabolites. We developed a multiplex LC-MS/MS method, using atmospheric pressure chemical ionization allowing the simultaneous determination in plasma of very-long-chain fatty acids, phytanic, pristanic, docosahexaenoic acids and di- and tri-hydroxycolestanoic bile acids. Two hundred microliters of plasma extracted with acetonitrile and 200μl extracted with hexane after an acid hydrolysis were combined, evaporated, dissolved in 10μl of methanol and analyzed. The acquisition was in negative-ion mode using multiple reaction monitoring. The method was validated analytically and clinically. Linearity was 0.1-200μmol/l for docosanoic, cis-13-docosenoic, tetracosanoic, cis-15-tetracosenoic and phytanic acids; 0.01-10μmol/l for hexacosanoic acid; 0.02-20μmol/l for di-hydroxycolestanoic, tri-hydroxycolestanoic and pristanic acids; 0.3-300μmol/l for docosahexaenoic acid. Intra-day and inter-day CVs were below 3.88 and 3.98 respectively for all compounds. Samples from patients with known peroxisomal disorders were compared with controls and the method allowed to confirm the diagnosis in all subjects with a 100% sensitivity. The advantage of this multiplex method is to allow in a single chromatographic run the simultaneous determination of a large number of peroxisome biomarkers with a simple preparative phase without derivatization. PMID:27189059

  17. Paired-ion electrospray ionization--triple quadrupole tandem mass spectrometry for quantification of anionic surfactants in waters.

    Science.gov (United States)

    Santos, Inês C; Guo, Hongyue; Mesquita, Raquel B R; Rangel, António O S S; Armstrong, Daniel W; Schug, Kevin A

    2015-10-01

    A new paired ion electrospray ionization tandem mass spectrometry method for determination of anionic surfactants in water samples was developed. In this method, dicationic ion-pairing reagents were complexed with monoanionic analytes to facilitate analyte detection in positive mode electrospray ionization - mass spectrometry. Single ion monitoring and selected reaction monitoring on a triple quadrupole instrument were performed and compared. Four dicationic reagents were tested for the determination of perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), sodium dodecyl sulfate (SDS), dodecylbenzene sulfonic acid (DBS), and stearic acid (SA), among other common anions. The obtained limits of detection were compared with those from previous literature. Solid phase extraction using a C18 cartridge was performed in order to eliminate matrix interferences. A literature review was compiled for the methods published between 2010 and 2015 for determination of anionic surfactants. The optimized method was more sensitive than previously developed methods with LOD values of 2.35, 35.4, 37.0, 1.68, and 0.675 pg for SDS, SA, DBS, PFOS, and PFOA, respectively. The developed method was effectively applied for the determination of anionic surfactants in different water samples such as bottled drinking water, cooking water, tap water, and wastewater. PMID:26078166

  18. Direct analysis by electrospray ionization tandem mass spectrometry of mixtures of phosphatidyldiacylglycerols from Lactobacillus.

    Science.gov (United States)

    Cabrera, G M; Murga, M L; de Valdez, G F; Seldes, A M

    2000-12-01

    Electrospray ionization followed by collision-induced dissociation in a quadrupole ion trap mass spectrometer of mixtures of deprotonated phosphatidyldiacylglycerols afforded a group of three diagnostic ions of convenient abundance for each phosphatidyldiacylglycerol (PG) present in the mixture. Thus, it was possible to determine unmistakably the identity and substitution positions (sn-1 or sn-2) for both acyl groups of each PG present in the mixture. The method also allows the study of isomeric mixtures of PG and mixtures containing minor amounts of some PG from crude extracts of Lactobacillus acidophillus. The present results improve those of previous studies using fast atom bombardment and electrospray ionization tanden mass spectrometry, in which it was reported that it was possible to differentiate the identity and position of the sn-2 acyl substituent only by the presence of one ion, with variable abundance. PMID:11180636

  19. Characterization and identification of iridoid glucosides, flavonoids and anthraquinones in Hedyotis diffusa by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Liu, E-Hu; Zhou, Ting; Li, Guo-Bin; Li, Jing; Huang, Xiu-Ning; Pan, Feng; Gao, Ning

    2012-01-01

    The multiple bioactive constituents in Hedyotis diffusa Willd. (H. diffusa) were extracted and characterized by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry (HPLC-ESI-MS(n)). The optimized separation condition was obtained using an Agilent ZorBax SB-C18 column (4.6×150 mm, 5 μm) and gradient elution with water (containing 0.1% formic acid) and acetonitrile (containing 0.1% formic acid), under which baseline separation for the majority of compounds was achieved. Among the compounds detected, 14 iridoid glucosides, 10 flavonoids, 7 anthraquinones, 1 coumarin and 1 triterpene were unambiguously identified or tentatively characterized based on their retention times and mass spectra in comparison with the data from standards or references. The fragmentation behavior for different types of constituents was also investigated, which could contribute to the elucidation of these constituents in H. diffusa. The present study reveals that even more iridoid glycosides were found in H. diffusa than hitherto assumed. The occurrence of two iridoid glucosides and five flavonoids in particular has not yet been described. This paper marks the first report on the structural characterization of chemical compounds in H. diffusa by a developed HPLC-ESI-MS(n) method. PMID:25940590

  20. Peroxy radical observations using chemical ionization mass spectrometry during TOPSE

    Science.gov (United States)

    Cantrell, Christopher A.; Edwards, G. D.; Stephens, S.; Mauldin, L.; Kosciuch, E.; Zondlo, M.; Eisele, F.

    2003-03-01

    Peroxy radicals (HO2 + RO2) were measured by chemical conversion-chemical ionization mass spectroscopy in the TOPSE (Tropospheric Ozone Production about the Spring Equinox) campaign that took place February through May 2000. Instrumentation for these measurements was deployed on the NCAR/NSF C-130 aircraft that flew at latitudes from 40 to 85°N, and altitudes from the surface to 7.5 km over the North American continent. The measurements demonstrate the evolution of photochemical activity as time progresses through the study period due to increases in free radical source rates. The increase in average peroxy radical concentration moves northward as the maximum solar elevation and length of sunlit days increase. HOxROx (HO2 + RO2) concentrations are distributed lognormally with means of 11.5 and 7.8 pptv for the middle-latitude band (MLB) and high-latitude band (HLB), respectively. The observations agree well on average with steady state derived concentrations; measurement-model concentration ratios are 1.04 (MLB) and 0.94 (HLB). Concentrations within a given latitude band and altitude region sometimes appear to increase with NOx concentrations, but this correlation nearly disappears at low and moderate NOx levels when the data are parsed by radical production rate; lower radical levels are observed at the highest NOx levels measured (near 1 ppbv). These data are compared with results from other recent observations utilizing a variety of platforms.

  1. Ion-molecule reactions of oxygenated chemical ionization reagents with vincamine.

    Science.gov (United States)

    Bauerle, G F; Hall, B J; Tran, N V; Brodbelt, J S

    1996-03-01

    The ion-molecule reactions of ions from acetone, dimethyl ether, 2-methoxyethanol, and vinyl methyl ether with vincamine were investigated. Reactions with dimethyl ether result in [M+13](+) and [M+45](+) products, reactions with 2-methoxyethanol produce [M+13](+) and [M+89](+) ions, and reactions with acetone or vinyl methyl ether ions generate predominantly [M+43](+) ions. Collision-activated dissociation and deuterium labeling experiments allowed speculation about the product structures and mechanisms of dissociation. The methylene substitution process was shown to occur at the hydroxyl oxygen and the phenyl ring of vincamine for dimethyl ether reactions, but the methylene substitution process was not favored at the hydroxyl oxygen for the 2-methoxyethanol reactions, instead favored at the 12 phenyl position. The reaction site is likely different for the 2-methoxyethanol ion due to its capability for secondary hydrogen-bonding interactions. For the [M+45](+) and [M+89](+) ions, evidence suggests that charge-remote fragmentation processes occur from these products. In general, the use of dimethyl ether ions or 2-methoxyethanol ions for ionmolecule reactions prove highly diagnostic for the characterization of vincamine; both molecular weight and structural information are obtained. Limits of detection for vincamine with dimethyl ether chemical ionization via this technique on a benchtop ion trap gas chromatography-tandem mass spectrometer are in the upper parts per trillion range. PMID:24203296

  2. Identification and Quantification of the Major Constituents in Egyptian Carob Extract by Liquid Chromatography–Electrospray Ionization-Tandem Mass Spectrometry

    OpenAIRE

    Asmaa Ibrahim Owis; El-Motaz Bellah El-Naggar

    2016-01-01

    Background: Carob - Ceratonia siliqua L., commonly known as St John's-bread or locust bean, family Fabaceae - is one of the most useful native Mediterranean trees. There is no data about the chromatography methods performed by high performance liquid chromatography (HPLC) for determining polyphenols in Egyptian carob pods. Objective: To establish a sensitive and specific liquid chromatography–electrospray ionization (ESI)-tandem mass spectrometry (MSn) methodology for the identification of th...

  3. Quantitative analysis of positional isomers of triacylglycerols via electrospray ionization tandem mass spectrometry of sodiated adducts.

    Science.gov (United States)

    Herrera, Lisandra Cubero; Potvin, Michael A; Melanson, Jeremy E

    2010-09-01

    Herein we report a reversed-phase high-performance liquid chromatography tandem mass spectrometry (RP-HPLC/MS/MS) method for the analysis of positional isomers of triacylglycerols (TAGs) in vegetable oils. The fragmentation behavior of [M + X](+) ions (X = NH(4), Li, Na or Ag) was studied on a quadrupole-time-of-flight (Q-TOF) mass spectrometer under low-energy collision-induced dissociation (CID) conditions. Mass spectra that were dependent on the X(+) ion and the nature and position of the acyl substituents were observed for four pairs of 'AAB/ABA'-type TAGs, namely PPO/POP, OOP/OPO, LLO/LOL and OOL/OLO (where P is 16:0, palmitic acid; O is 18:1, oleic acid; and L is 18:2, linoleic acid). For the majority of [M + X](+) adducts, the loss of the fatty acid in the outer positions (sn-1 or sn-3) was favored over the loss in the central position (sn-2), which enabled the determination of the fractional abundance of the isomers. Ratios of the intensity of fragment ions at various AAB/ABA compositions produced linear calibration curves with positive slopes, comparable to those obtained traditionally by ESI-MS/MS of [M + NH(4)](+) adducts. The only exceptions were the [M + Ag](+) adducts of the PPO/POP system, which produced calibration curves with negative slopes. Sodium adducts provided the most consistent level of isomeric discrimination for the TAGs studied and also offered the most convenience in that they required no additive to the mobile phase. Therefore, calibration curve data derived from [M + Na](+) adducts were applied to the quantification of TAG regioisomers in sunflower and olive oils. The regiospecific analysis showed that palmitic acid was typically located at positions sn-1 or sn-3, whereas unsaturated fatty acids, oleic and linoleic acids were mostly found at the sn-2 position. PMID:20814981

  4. Determination of benzotriazole corrosion inhibitors from aqueous environmental samples by liquid chromatography-electrospray ionization-tandem mass spectrometry.

    Science.gov (United States)

    Weiss, Stefan; Reemtsma, Thorsten

    2005-11-15

    The first method for the determination of commonly used corrosion inhibitors in environmental water samples by liquid chromatography-electrospray ionization-tandem mass spectrometry is presented. Benzotriazole (BTri) and the two isomers of tolyltriazole (5- and 4-TTri) are separated in an isocratic run. By gradient elution, BTri, 4-TTri, 5-TTri, and xylyltriazole can be determined simultaneously with three benzothiazoles, but here TTri isomers coelute. The instrumental detection limit of 2 pg allows the determination of the three most important benzotriazoles from municipal wastewater and most surface waters by direct injection into the HPLC system without previous enrichment. When solid-phase extraction is employed with mean recovery rates of 95-113%, the limit of quantification for benzotriazoles range from 10 ng/L in groundwater to 25 ng/L in untreated wastewater. BTri and TTri were determined in municipal wastewater in microgram per liter concentrations. Elimination in wastewater treatment appears to be poor, and BTri and TTri can be followed through a water cycle from treated municipal wastewater through surface water to bank filtrate used for drinking water production. The TTri isomers show markedly different biodegradation behavior with 4-TTri being more stable. PMID:16285694

  5. Identification of cephapirin metabolites and degradants in bovine milk by electrospray ionization--ion trap tandem mass spectrometry.

    Science.gov (United States)

    Heller, D N; Kaplan, D A; Rummel, N G; von Bredow, J

    2000-12-01

    Liquid chromatography-ion trap tandem mass spectrometry (LC-MS/MS) with electrospray ionization was used to identify cephapirin metabolites and degradants in milk from cows dosed with cephapirin. The milk was extracted according to a previously published procedure. Structures for various components were tentatively identified by their molecular weight, product ion mass spectra, and/or correspondence to standard mass spectra. These components may have occurred as metabolites or as degradants that occurred on storage or during extraction. Compounds identified in the milk included cephapirin, desacetylcephapirin, cephapirin lactone, hydrolyzed cephapirin, and a reduced cephapirin lactone that has not previously been reported. Methylcephapirin was also identified, possibly as a trace contaminant in the formulation. Analysis of incurred milk extracts showed that cephapirin and desacetylcephapirin are the major residues in milk. Desacetylcephapirin residues persisted about as long as the parent drug. The detection limit for both residues by LC-MS/MS was approximately 1 ng/mL in milk. These results have implications for microbiological methods or rapid test kits, if such methods or kits respond to cephapirin metabolites and degradants present in the milk. PMID:11141270

  6. Elucidating collision induced dissociation products and reaction mechanisms of protonated uracil by coupling chemical dynamics simulations with tandem mass spectrometry experiments.

    Science.gov (United States)

    Molina, Estefanía Rossich; Ortiz, Daniel; Salpin, Jean-Yves; Spezia, Riccardo

    2015-12-01

    In this study we have coupled mixed quantum-classical (quantum mechanics/molecular mechanics) direct chemical dynamics simulations with electrospray ionization/tandem mass spectrometry experiments in order to achieve a deeper understanding of the fragmentation mechanisms occurring during the collision induced dissociation of gaseous protonated uracil. Using this approach, we were able to successfully characterize the fragmentation pathways corresponding to ammonia loss (m/z 96), water loss (m/z 95) and cyanic or isocyanic acid loss (m/z 70). Furthermore, we also performed experiments with isotopic labeling completing the fragmentation picture. Remarkably, fragmentation mechanisms obtained from chemical dynamics simulations are consistent with those deduced from isotopic labeling. PMID:26634967

  7. Chemical Aspects of the Extractive Methods of Ambient Ionization Mass Spectrometry

    Science.gov (United States)

    Badu-Tawiah, Abraham K.; Eberlin, Livia S.; Ouyang, Zheng; Cooks, R. Graham

    2013-04-01

    Ambient ionization techniques allow complex chemical samples to be analyzed in their native state with minimal sample preparation. This brings the obvious advantages of simplicity, speed, and versatility to mass spectrometry: Desorption electrospray ionization (DESI), for example, is used in chemical imaging for tumor margin diagnosis. This review on the extractive methods of ambient ionization focuses on chemical aspects, mechanistic considerations, and the accelerated chemical reactions occurring in charged liquid droplets generated in the spray process. DESI uses high-velocity solvent droplets to extract analytes from surfaces. Nano-DESI employs liquid microjunctions for analyte dissolution, whereas paper-spray ionization uses DC potentials applied to wet porous material such as paper or biological tissue to field emit charged analyte-containing solvent droplets. These methods also operate in a reactive mode in which added reagents allow derivatization during ionization. The accelerated reaction rates seen in charged microdroplets are useful in small-scale rapid chemical synthesis.

  8. Analysis of acylcarnitine profiles in umbilical cord blood and during the early neonatal period by electrospray ionization tandem mass spectrometry

    International Nuclear Information System (INIS)

    Acylcarnitine profiling by electrospray ionization tandem mass spectrometry (ESI-MS/MS) is a potent tool for the diagnosis and screening of fatty acid oxidation and organic acid disorders. Few studies have analyzed free carnitine and acylcarnitines in dried blood spots (DBS) of umbilical cord blood (CB) and the postnatal changes in the concentrations of these analytes. We have investigated these metabolites in healthy exclusively breastfed neonates and examined possible effects of birth weight and gestational age. DBS of CB were collected from 162 adequate for gestational age neonates. Paired DBS of heel-prick blood were collected 4-8 days after birth from 106 of these neonates, the majority exclusively breastfed. Methanol extracts of DBS with deuterium-labeled internal standards were derivatized before analysis by ESI-MS/MS. Most of the analytes were measured using a full-scan method. The levels of the major long-chain acylcarnitines, palmitoylcarnitine, stearoylcarnitine, and oleoylcarnitine, increased by 27, 12, and 109%, respectively, in the first week of life. Free carnitine and acetylcarnitine had a modest increase: 8 and 11%, respectively. Propionylcarnitine presented a different behavior, decreasing 9% during the period. The correlations between birth weight or gestational age and the concentrations of the analytes in DBS were weak (r ≤ 0.20) or nonsignificant. Adaptation to breast milk as the sole source of nutrients can explain the increase of these metabolites along the early neonatal period. Acylcarnitine profiling in CB should have a role in the early detection of metabolic disorders in high-risk neonates

  9. Analysis of acylcarnitine profiles in umbilical cord blood and during the early neonatal period by electrospray ionization tandem mass spectrometry

    Directory of Open Access Journals (Sweden)

    E. Vieira Neto

    2012-06-01

    Full Text Available Acylcarnitine profiling by electrospray ionization tandem mass spectrometry (ESI-MS/MS is a potent tool for the diagnosis and screening of fatty acid oxidation and organic acid disorders. Few studies have analyzed free carnitine and acylcarnitines in dried blood spots (DBS of umbilical cord blood (CB and the postnatal changes in the concentrations of these analytes. We have investigated these metabolites in healthy exclusively breastfed neonates and examined possible effects of birth weight and gestational age. DBS of CB were collected from 162 adequate for gestational age neonates. Paired DBS of heel-prick blood were collected 4-8 days after birth from 106 of these neonates, the majority exclusively breastfed. Methanol extracts of DBS with deuterium-labeled internal standards were derivatized before analysis by ESI-MS/MS. Most of the analytes were measured using a full-scan method. The levels of the major long-chain acylcarnitines, palmitoylcarnitine, stearoylcarnitine, and oleoylcarnitine, increased by 27, 12, and 109%, respectively, in the first week of life. Free carnitine and acetylcarnitine had a modest increase: 8 and 11%, respectively. Propionylcarnitine presented a different behavior, decreasing 9% during the period. The correlations between birth weight or gestational age and the concentrations of the analytes in DBS were weak (r £ 0.20 or nonsignificant. Adaptation to breast milk as the sole source of nutrients can explain the increase of these metabolites along the early neonatal period. Acylcarnitine profiling in CB should have a role in the early detection of metabolic disorders in high-risk neonates.

  10. Analysis of acylcarnitine profiles in umbilical cord blood and during the early neonatal period by electrospray ionization tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Vieira Neto, E. [Serviço de Genética Médica, Instituto de Puericultura e Pediatria Martagão Gesteira, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ (Brazil); Laboratório Diagnósticos Laboratoriais Especializados, Rio de Janeiro, RJ (Brazil); Fonseca, A.A.; Almeida, R.F. [Laboratório Diagnósticos Laboratoriais Especializados, Rio de Janeiro, RJ (Brazil); Figueiredo, M.P.; Porto, M.A.S. [Maternidade Escola, Rio de Janeiro, RJ (Brazil); Ribeiro, M.G. [Serviço de Genética Médica, Instituto de Puericultura e Pediatria Martagão Gesteira, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ (Brazil)

    2012-04-13

    Acylcarnitine profiling by electrospray ionization tandem mass spectrometry (ESI-MS/MS) is a potent tool for the diagnosis and screening of fatty acid oxidation and organic acid disorders. Few studies have analyzed free carnitine and acylcarnitines in dried blood spots (DBS) of umbilical cord blood (CB) and the postnatal changes in the concentrations of these analytes. We have investigated these metabolites in healthy exclusively breastfed neonates and examined possible effects of birth weight and gestational age. DBS of CB were collected from 162 adequate for gestational age neonates. Paired DBS of heel-prick blood were collected 4-8 days after birth from 106 of these neonates, the majority exclusively breastfed. Methanol extracts of DBS with deuterium-labeled internal standards were derivatized before analysis by ESI-MS/MS. Most of the analytes were measured using a full-scan method. The levels of the major long-chain acylcarnitines, palmitoylcarnitine, stearoylcarnitine, and oleoylcarnitine, increased by 27, 12, and 109%, respectively, in the first week of life. Free carnitine and acetylcarnitine had a modest increase: 8 and 11%, respectively. Propionylcarnitine presented a different behavior, decreasing 9% during the period. The correlations between birth weight or gestational age and the concentrations of the analytes in DBS were weak (r ≤ 0.20) or nonsignificant. Adaptation to breast milk as the sole source of nutrients can explain the increase of these metabolites along the early neonatal period. Acylcarnitine profiling in CB should have a role in the early detection of metabolic disorders in high-risk neonates.

  11. Rapid and sensitive hormonal profiling of complex plant samples by liquid chromatography coupled to electrospray ionization tandem mass spectrometry

    Directory of Open Access Journals (Sweden)

    Müller Maren

    2011-11-01

    Full Text Available Abstract Background Plant hormones play a pivotal role in several physiological processes during a plant's life cycle, from germination to senescence, and the determination of endogenous concentrations of hormones is essential to elucidate the role of a particular hormone in any physiological process. Availability of a sensitive and rapid method to quantify multiple classes of hormones simultaneously will greatly facilitate the investigation of signaling networks in controlling specific developmental pathways and physiological responses. Due to the presence of hormones at very low concentrations in plant tissues (10-9 M to 10-6 M and their different chemistries, the development of a high-throughput and comprehensive method for the determination of hormones is challenging. Results The present work reports a rapid, specific and sensitive method using ultrahigh-performance liquid chromatography coupled to electrospray ionization tandem spectrometry (UPLC/ESI-MS/MS to analyze quantitatively the major hormones found in plant tissues within six minutes, including auxins, cytokinins, gibberellins, abscisic acid, 1-amino-cyclopropane-1-carboxyic acid (the ethylene precursor, jasmonic acid and salicylic acid. Sample preparation, extraction procedures and UPLC-MS/MS conditions were optimized for the determination of all plant hormones and are summarized in a schematic extraction diagram for the analysis of small amounts of plant material without time-consuming additional steps such as purification, sample drying or re-suspension. Conclusions This new method is applicable to the analysis of dynamic changes in endogenous concentrations of hormones to study plant developmental processes or plant responses to biotic and abiotic stresses in complex tissues. An example is shown in which a hormone profiling is obtained from leaves of plants exposed to salt stress in the aromatic plant, Rosmarinus officinalis.

  12. Analysis of abused drugs by selected ion monitoring: quantitative comparison of electron impact and chemical ionization

    International Nuclear Information System (INIS)

    A comparison was made of the relative sensitivities of electron impact and chemical ionization when used for selected ion monitoring analysis of commonly abused drugs. For most of the drugs examined chemical ionization using ammonia as the reactant gas gave the largest single m/e ion current response per unit weight of sample. However, if maximum sensitivity is desired it is important to evaluate electron impact and chemical ionization with respect to both maximum response and degree of interference from background and endogenous materials

  13. Chemical engineering challenges in driving thermochemical hydrogen processes with the tandem mirror reactor

    International Nuclear Information System (INIS)

    The Tandem Mirror Reactor is described and compared with Tokamaks, both from a basic physics viewpoint and from the suitability of the respective reactor for synfuel production. Differences and similarities between the TMR as an electricity producer or a synfuel producer are also cited. The Thermochemical cycle chosen to link with the fusion energy source is the General Atomic Sulfur-Iodine Cycle, which is a purely thermal-driven process with no electrochemical steps. There are real chemical engineering challenges of getting this high quality heat into the large thermochemical plant in an efficient manner. We illustrate with some of our approaches to providing process heat via liquid sodium to drive a 1050 K, highly-endothermic, catalytic and fluidized-bed SO3 Decomposition Reactor. The technical, economic, and safety tradeoffs that arise are discussed

  14. Applications of a versatile technique for trace analysis: atmospheric pressure negative chemical ionization.

    OpenAIRE

    Thomson, B A; Davidson, W R; Lovett, A M

    1980-01-01

    The ability to use ambient air as a carrier and reagent gas in an atmospheric pressure chemical ionization source allows instantaneous air analysis to be combined with hypersensitivity toward a wide variety of compounds. The TAGA (Trace Atmospheric Gas Analyser) is an instrument which is designed to use both positive and negative atmospheric pressure chemical ionization (APCI) for trace gas analysis; this paper describes several applications of negative APCI which demonstrates that the techni...

  15. Choosing between atmospheric pressure chemical ionization and electrospray ionization interfaces for the HPLC/MS analysis of pesticides

    Science.gov (United States)

    Thurman, E.M.; Ferrer, I.; Barcelo, D.

    2001-01-01

    An evaluation of over 75 pesticides by high-performance liquid chromatography/mass spectrometry (HPLC/MS) clearly shows that different classes of pesticides are more sensitive using either atmospheric pressure chemical ionization (APCI) or electrospray ionization (ESI). For example, neutral and basic pesticides (phenylureas, triazines) are more sensitive using APCI (especially positive ion). While cationic and anionic herbicides (bipyridylium ions, sulfonic acids) are more sensitive using ESI (especially negative ion). These data are expressed graphically in a figure called an ionization-continuum diagram, which shows that protonation in the gas phase (proton affinity) and polarity in solution, expressed as proton addition or subtraction (pKa), is useful in selecting APCI or ESI. Furthermore, sodium adduct formation commonly occurs using positive ion ESI but not using positive ion APCI, which reflects the different mechanisms of ionization and strengthens the usefulness of the ionization-continuum diagram. The data also show that the concept of "wrong-way around" ESI (the sensitivity of acidic pesticides in an acidic mobile phase) is a useful modification of simple pKa theory for mobile-phase selection. Finally, this finding is used to enhance the chromatographic separation of oxanilic and sulfonic acid herbicides while maintaining good sensitivity in LC/MS using ESI negative.

  16. Determination of kava lactones in food supplements by liquid chromatography-atmospheric pressure chemical ionisation tandem mass spectrometry

    NARCIS (Netherlands)

    Bobeldijk, I.; Boonzaaijer, G.; Spies-Faber, E.J.; Vaes, W.H.J.

    2005-01-01

    Reversed-phase liquid chromatography and detection with atmospheric pressure chemical ionisation tandem mass spectrometry was used for the determination of kava extracts in herbal mixtures. One percent of kava extract can be detected, corresponding to approximately 0.05-0.2 mg/g of the individual ka

  17. Role of ionizing radiation in chemical evolution studies

    International Nuclear Information System (INIS)

    The purpose of this paper is to emphasize the role of ionizing radiation in radiation-induced reactions in prebiotic chemistry. The use of ionizing radiation as an energy source is based on its unique qualities, its specific manner of energy deposition and its abundance in the Earth's crust. As an example of radiation-induced reactions, the radiolysis of malonic acid was investigated. Malonic acid is converted into other carboxylic acids. The results obtained have been correlated with the ready formation of this compound in prebiotic experiments. (author)

  18. Simultaneous Determination of Eight Ginsenosides in Rat Plasma by Liquid Chromatography–Electrospray Ionization Tandem Mass Spectrometry: Application to Their Pharmacokinetics

    OpenAIRE

    Li-Yuan Ma; You-Bo Zhang; Qi-Le Zhou; Yan-Fang Yang; Xiu-Wei Yang

    2015-01-01

    A high-performance liquid chromatography–electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) method was successfully developed and validated for the identification and determination of eight ginsenosides: ginsenoside Rg1 (1); 20(S)-ginsenoside Rh1 (2); 20(S)-ginsenoside Rg2 (3); 20(R)-ginsenoside Rh1 (4); 20(R)-ginsenoside Rg2 (5); ginsenoside Rd (6); 20(S)-ginsenoside Rg3 (7); and 20(R)-ginsenoside Rg3 (8) in rat plasma. The established rapid method had high linearity, selectivit...

  19. Chemical-ionization visible and ultraviolet gas lasers: A concept

    Science.gov (United States)

    Laudenslager, J. B.

    1975-01-01

    Charge-transfer reactions or Penning ionization reactions are used to produce population inversions between electronic states of molecular ions which should result in stimulated emission in ultraviolet and visible regions. Such lasers could be used in study of short-lived reaction intermediates, crystal structure and scattering, and photolysis.

  20. Analysis of caged xanthones from the resin of Garcinia hanburyi using ultra-performance liquid chromatography/electrospray ionization quadrupole time-of-flight tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Zhou Yan [Hong Kong Jockey Club Institute of Chinese Medicine, Shatin, Hong Kong (China); Liu Xin [Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041, Sichuan Province (China); Yang Jing [School of Chemistry and Chemical Technology, Shanghai Jiao Tong University, Shanghai 200240 (China); Han Quanbin; Song Jingzheng; Li Songlin; Qiao Chunfeng [Hong Kong Jockey Club Institute of Chinese Medicine, Shatin, Hong Kong (China); Ding Lisheng [Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041, Sichuan Province (China)], E-mail: lsding@cib.ac.cn; Xu Hongxi [Hong Kong Jockey Club Institute of Chinese Medicine, Shatin, Hong Kong (China)], E-mail: xuhongxi@hkjcicm.org

    2008-11-23

    On-line ultra high-performance liquid chromatography (UHPLC) coupled with electrospray quadrupole time-of-flight tandem mass spectrometry (ESI-QTOF-MS/MS/MS) has been developed for the analysis of a series of caged xanthones in the resin of Garcinia hanburyi. The fragmentation of protonated molecular ions for 12 known cadged xanthones was carried out using low-energy collision-induced electrospray ionization tandem mass spectrometry. It was found that Retro-Diels-Alder rearrangement occurred in the CID processes and produced the characteristic fragment ions, which are especially valuable for the identification of this class of xanthones. The fragmentation differential between some cis-, trans-isomers was uncovered. Computation methods were utilized to rationalize the observed MS behaviors. On-line UHPLC-ESI-MS/MS/MS method has proved to be rapid and efficient in that within 6 min, 15 caged scaffold xanthones, including three pairs of epimers and four pairs of isomers in gamboges, were effectively separated and identified. Among them, two known, namely isogambogenin (13) and isomorellinol (14) and one likely new caged Garcinia xanthones from the Garcinia hanburyi were tentatively characterized based on the tandem mass spectra of known ones.

  1. Analysis of caged xanthones from the resin of Garcinia hanburyi using ultra-performance liquid chromatography/electrospray ionization quadrupole time-of-flight tandem mass spectrometry

    International Nuclear Information System (INIS)

    On-line ultra high-performance liquid chromatography (UHPLC) coupled with electrospray quadrupole time-of-flight tandem mass spectrometry (ESI-QTOF-MS/MS/MS) has been developed for the analysis of a series of caged xanthones in the resin of Garcinia hanburyi. The fragmentation of protonated molecular ions for 12 known cadged xanthones was carried out using low-energy collision-induced electrospray ionization tandem mass spectrometry. It was found that Retro-Diels-Alder rearrangement occurred in the CID processes and produced the characteristic fragment ions, which are especially valuable for the identification of this class of xanthones. The fragmentation differential between some cis-, trans-isomers was uncovered. Computation methods were utilized to rationalize the observed MS behaviors. On-line UHPLC-ESI-MS/MS/MS method has proved to be rapid and efficient in that within 6 min, 15 caged scaffold xanthones, including three pairs of epimers and four pairs of isomers in gamboges, were effectively separated and identified. Among them, two known, namely isogambogenin (13) and isomorellinol (14) and one likely new caged Garcinia xanthones from the Garcinia hanburyi were tentatively characterized based on the tandem mass spectra of known ones

  2. Characterization of typical chemical background interferences in atmospheric pressure ionization liquid chromatography-mass spectrometry

    NARCIS (Netherlands)

    Guo, Xinghua; Bruins, Andries P.; Covey, Thomas R.

    2006-01-01

    The structures and origins of typical chemical background noise ions in positive atmospheric pressure ionization liquid chromatography/mass spectrometry (API LC/MS) are investigated and summarized in this study. This was done by classifying chemical background ions using precursor and product ion sc

  3. Effect of pH and dissociation on the fate and exposure of ionizable chemicals

    DEFF Research Database (Denmark)

    Franco, Antonio; Trapp, Stefan

    2010-01-01

    Ionizable organic chemicals comprise an important fraction of pharmaceuticals, pesticides as well as industrial chemicals. It has been estimated that 33% of the preregistered REACH substances is mostly ionized at pH 7. To extend the appliccability of existing exposure models, a Multimedia Activity...... Model for Ionics (MAMI) was recently developed and tested. In the present study, the impact of the parameters describing ionization was assessed by performing the sensitivity and the uncertainty analysis on MAMI for the acids 2,4-D, pentachlorophenol, bisphenol-A, perfluorooctanoic acid and the bases...... parameters. The sensitivity analysis showed that the parameters describing ionization, pH and the dissociation constant (pKa), are among the most sensitive model parameters. The uncertainty analysis, however, indicated that these parameters are not the major source of uncertainty, which statistically...

  4. Chemical changes in food packaging resulting from ionizing irradiation

    International Nuclear Information System (INIS)

    Recent approvals of food irradiation processes by the U.S. Food and Drug Administration have led to a search for packaging approved for use with ionizing radiation. Though 13 packaging materials were approved several years ago as food contactants for gamma irradiation up to 10 kGy at refrigeration temperatures and 4 packaging materials were approved for up to 60 kGy at cryogenic temperatures, no currently used packaging is approved for irradiated foods. Extensive research was conducted by the U.S. Army and others on the suitability of both flexible packaging and metal cans for packaging irradiated foods. The results of the studies of packaging for irradiated foods will be described and discussed in context of currently used packaging materials for non-irradiated meats and poultry

  5. Direct Laser Ablation and Ionization of Solids for Chemical Analysis by Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Holt, J K; Nelson, E J; Klunder, G L

    2005-09-02

    A laser ablation/ionization mass spectrometer system is described for the direct chemical analysis of solids. An Nd:YAG laser is used for ablation and ionization of the sample in a quadrupole ion trap operated in an ion-storage (IS) mode that is coupled with a reflectron time-of-flight mass spectrometer (TOF-MS). Single pulse experiments have demonstrated simultaneous detection of up to 14 elements present in glasses in the ppm range. However, detection of the components has produced non-stoichiometric results due to difference in ionization potentials and fractionation effects. Time-of-flight secondary ionization mass spectrometry (TOF-SIMS) was used to spatially map elemental species on the surface and provide further evidence of fractionation effects. Resolution (m/Dm) of 1500 and detection limits of approximately 10 pg have been achieved with a single laser pulse. The system configuration and related operating principles for accurately measuring low concentrations of isotopes are described.

  6. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    Science.gov (United States)

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-04-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt-1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion-molecule reactions likely proceed through a combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.

  7. Relationships between structure, ionization profile and sensitivity of exogenous anabolic steroids under electrospray ionization and analysis in human urine using liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

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

    2016-04-01

    The relationships between the ionization profile, sensitivity, and structures of 64 exogenous anabolic steroids (groups I-IV) was investigated under electrospray ionization (ESI) conditions. The target analytes were ionized as [M + H](+) or [M + H-nH2 O](+) in the positive mode, and these ions were used as precursor ions for selected reaction monitoring analysis. The collision energy and Q3 ions were optimized based on the sensitivity and selectivity. The limits of detection (LODs) were 0.05-20 ng/mL for the 64 steroids. The LODs for 38 compounds, 14 compounds and 12 compounds were in the range of 0.05-1, 2-5 and 10-20 ng/mL, respectively. Steroids including the conjugated keto-functional group at C3 showed good proton affinity and stability, and generated the [M + H](+) ion as the most abundant precursor ion. In addition, the LODs of steroids using the [M + H](+) ion as the precursor ion were mostly distributed at low concentrations. In contrast, steroids containing conjugated/unconjugated hydroxyl functional groups at C3 generated [M + H - H2 O](+) or [M + H - 2H2 O](+) ions, and these steroids showed relatively high LODs owing to poor stability and multiple ion formation. An LC-MS/MS method based on the present ionization profile was developed and validated for the determination of 78 steroids (groups I-V) in human urine. PMID:26268571

  8. High-performance liquid chromatography/high-resolution multiple stage tandem mass spectrometry using negative-ion-mode hydroxide-doped electrospray ionization for the characterization of lignin degradation products.

    Science.gov (United States)

    Owen, Benjamin C; Haupert, Laura J; Jarrell, Tiffany M; Marcum, Christopher L; Parsell, Trenton H; Abu-Omar, Mahdi M; Bozell, Joseph J; Black, Stuart K; Kenttämaa, Hilkka I

    2012-07-17

    In the search for a replacement for fossil fuel and the valuable chemicals currently obtained from crude oil, lignocellulosic biomass has become a promising candidate as an alternative biorenewable source for crude oil. Hence, many research efforts focus on the extraction, degradation, and catalytic transformation of lignin, hemicellulose, and cellulose. Unfortunately, these processes result in the production of very complex mixtures. Further, while methods have been developed for the analysis of mixtures of oligosaccharides, this is not true for the complex mixtures generated upon degradation of lignin. For example, high-performance liquid chromatography/multiple stage tandem mass spectrometry (HPLC/MS(n)), a tool proven to be invaluable in the analysis of complex mixtures derived from many other biopolymers, such as proteins and DNA, has not been implemented for lignin degradation products. In this study, we have developed an HPLC separation method for lignin degradation products that is amenable to negative-ion-mode electrospray ionization (ESI doped with NaOH), the best method identified thus far for ionization of lignin-related model compounds without fragmentation. The separated and ionized compounds are then analyzed by MS(3) experiments to obtain detailed structural information while simultaneously performing high-resolution measurements to determine their elemental compositions in the two parts of a commercial linear quadrupole ion trap/Fourier-transform ion cyclotron resonance mass spectrometer. A lignin degradation product mixture was analyzed using this method, and molecular structures were proposed for some components. This methodology significantly improves the ability to analyze complex product mixtures that result from degraded lignin. PMID:22746183

  9. Top-down proteomic identification of Shiga toxin 2 subtypes from Shiga toxin-producing Escherichia coli by Matrix-Assisted Laser Desorption Ionization-Tandem Time of Flight mass spectrometry

    Science.gov (United States)

    We have analyzed 26 Shiga toxin-producing Escherichia coli (STEC) strains for Shiga toxin 2 (Stx2) production using matrix-assisted laser desorption/ionization time-of-flight-time-of-flight tandem mass spectrometry (MALDI-TOF-TOF-MS/MS) and top-down proteomic analysis. STEC strains were induced to ...

  10. 牛膝中三萜皂甙类化合物的电喷雾质谱研究%Studies on Triterpene Saponin From Achyranthes bientata BI by Electrospray Ionization Tandem Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    梁勇; 方昆阳; 郭宝江; 梁冠洪; 宋艳平

    2004-01-01

    AchyranthosideI and Achyranthoside Ⅱ which were considered to be effective constituents from Achyranthes bientata BI were identified by electrospray tandem ionization mass spectrometric (ESI-MSn) methods after macro-porous adsorbent chromatographic separation. Their characteristic mass spectra can be use as fingerprint for the identification of AchyranthosideI and Achyranthoside Ⅱ . This method is simple .,rapid and highly sensitive.

  11. Development and comparison of two multiresidue methods for the analysis of 17 mycotoxins in cereals by liquid chromatography electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Desmarchelier, Aurelien; Oberson, Jean-Marie; Tella, Patricia; Gremaud, Eric; Seefelder, Walburga; Mottier, Pascal

    2010-07-14

    Two multiresidue methods based on different extraction procedures have been developed and compared for the liquid chromatography electrospray ionization tandem mass spectrometry analysis of 17 mycotoxins including ochratoxin A, aflatoxins (B(1), B(2), G(1), and G(2)), zearalenone, fumonisins (B(1) and B(2)), T-2 toxin, HT-2 toxin, nivalenol, deoxynivalenol, 3- and 15-acetyldeoxynivalenol, fusarenon-X, diacetoxyscirpenol, and neosolaniol in cereal-based commodities. The extraction procedures considered were a QuEChERS-like method and one using accelerated solvent extraction (ASE). Both extraction procedures gave similar performances in terms of linearity (r(2) > 0.98) and precision (both RSD(r) and RSD(iR) sample throughput as compared to the ASE method. PMID:20527950

  12. Can clouds enhance long-range transport of low volatile, ionizable and surface-active chemicals?

    DEFF Research Database (Denmark)

    Franco, Antonio; Trapp, Stefan

    2011-01-01

    potential of non-volatile substances. The liquid water content of clouds and the high specific surface of frozen or liquid cloud droplets can significantly contribute to the total activity capacity (i.e. the capacity to sorb chemicals) of the atmosphere for non-volatile, ionizable and surface active...... volatile or ionizable chemicals to investigate the potential of clouds to enhance the atmospheric transport potential. Probability density functions were derived for input substance properties and environmental parameters to quantify uncertainty and variability and probabilistic simulations at steady state...... were run for a constant emission to the atmospheric boundary layer to identify key model inputs. The degradation rate, the duration of dry and wet periods and the parameters describing air-water bulk partitioning (KAW and T) and ionization (pKa and pH) determine the residence time in the ABL. In the...

  13. Use of the chemical ionization technique for deltametrin by GC/MS

    International Nuclear Information System (INIS)

    An analytical methodology for the determination of synthetic pyrethroid deltametrin is described. The gas chromatography coupled with the mass spectrometry GC/MS technique, using the chemical ionization technique as ions generator is used for deltametrin analysis, and methane is used as reactant gas chemical ionization. Impurities were detected with the electron impact ionization technique. Dichloromethane grade HPLC was used as deltametrin solvent.Deltametrin concentration in 1 μg/ml were detected by injecting 1 μl sample in the GC/MS. From the obtained chromatograms it is observed a deltametrin molecule retention time of 42.5 min in chromatography column. The mass spectra were obtained with mass intervals between 40 and 620 u.m.a., with 1 u.m.a. resolution. Details of the sample preparation are presented. (author). 10 refs., 3 figs., 1 tab

  14. Quantitative analysis of abused drugs in physiological fluids by gas chromatography/chemical ionization mass spectrometry

    International Nuclear Information System (INIS)

    Methods have been developed for quantitative analysis of commonly abused drugs in physiological fluids using gas chromatography/chemical ionization mass spectrometry. The methods are being evaluated in volunteer analytical and toxicological laboratories, and analytical manuals describing the methods are being prepared. The specific drug and metabolites included in this program are: Δ9-tetrahydrocannabinol, methadone, phencyclidine, methaqualone, morphine, amphetamine, methamphetamine, mescaline, 2,5-dimethoxy-4-methyl amphetamine, cocaine, benzoylecgonine, diazepam, and N-desmethyldiazepam. The current analytical methods utilize relatively conventional instrumentation and procedures, and are capable of measuring drug concentrations as low as 1 ng/ml. Various newer techniques such as sample clean-up by high performance liquid chromatography, separation by glass capillary chromatography, and ionization by negative ion chemical ionization are being investigated with respect to their potential for achieving higher sensitivity and specificity, as well as their ability to facilitate simultaneous analysis of more than one drug and metabolite. (Auth.)

  15. Determination of phosphatidylethanolamine molecular species in various food matrices by liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS2).

    Science.gov (United States)

    Zhou, Li; Zhao, Minjie; Ennahar, Saïd; Bindler, Françoise; Marchioni, Eric

    2012-04-01

    A liquid chromatographic-electrospray ionization-tandem mass spectrometric (LC-ESI-MS(2)) method has been developed for determination of the molecular species of phosphatidylethanolamine (PE) in four food matrices (soy, egg yolk, ox liver, and krill oil). The extraction and purification method consisted of a pressurized liquid extraction procedure for total lipid (TL) extraction, purification of phospholipids (PLs) by adsorption on a silica gel column, and separation of PL classes by semi-preparative normal-phase HPLC. Separation and identification of PE molecular species were performed by reversed-phase HPLC coupled with electrospray ionization tandem mass spectrometry (ESI-MS(2)). Methanol containing 5 mmol L(-1) ammonium formate was used as the mobile phase. A variety of PE molecular species were detected in the four food matrices. (C16:0-C18:2)PE, (C18:2-C18:2)PE, and (C16:0-C18:1)PE were the major PE molecular species in soy. Egg yolk PE contained (C16:0-C18:1)PE, (C18:0-C18:1)PE, (C18:0-C18:2)PE, and (C16:0-C18:2)PE as the major molecular species. Ox liver PE was rich in the species (C18:0-C18:1)PE, (C18:0-C20:4)PE, and (C18:0-C18:2)PE. Finally, krill oil which was particularly rich in (C16:0(alkyl)-C22:6(acyl))plasmanylethanolamine (PakE), (C16:0-C22:6)PE, and (C16:0-C20:5)PE, seemed to be an interesting potential source for supplementation of food with eicosapentaenoic acid and docosahexaenoic acid. PMID:22349329

  16. Instrumental aspects of positive and negative ion chemical ionization mass spectrometry.

    OpenAIRE

    Stafford, G C

    1980-01-01

    Differences in recording positive and negative ion chemical ionization mass spectra on a quadrupole mass spectrometer are discussed. An analog positive and negative ion electron multiplier detector is described which is well suited for a quadrupole instrument. This detector significantly reduces baseline noise in the negative ion mode and improves positive ion high mass sensitivity.

  17. Real-Time Flavor Release from French Fries Using Atmospheric Pressure Chemical Ionization-Mass Spectrometry

    NARCIS (Netherlands)

    Loon, W.A.M.; Linssen, J.P.H.; Boelrijk, A.E.M.; Burgering, M.J.M.; Voragen, A.G.J.

    2005-01-01

    Flavor release from French fries was measured with atmospheric pressure chemical ionization-mass spectrometry (APCI-MS) using both assessors (in vivo) and a mouth model system (in vitro). Several volatiles measured with APCI were identified with MS-MS. The effect of frying time, salt addition, and a

  18. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    OpenAIRE

    L. Rondo; Flagan, R. C.

    2016-01-01

    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H_2SO_4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantita...

  19. Self-Aspirated Atmospheric Pressure Chemical Ionization Source for Direct Sampling of Analytes on Surfaces and in Liquid Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Asano, Keiji G [ORNL; Ford, Michael J [ORNL; Tomkins, Bruce A [ORNL; Van Berkel, Gary J [ORNL

    2005-01-01

    A self-aspirating heated nebulizer probe is described and demonstrated for use in the direct analysis of analytes on surfaces and in liquid samples by atmospheric pressure chemical ionization (APCI) mass spectrometry. Functionality and performance of the probe as a self-aspirating APCI source is demonstrated using reserpine and progesterone as test compounds. The utility of the probe to sample analytes directly from surfaces was demonstrated first by scanning development lanes of a reversed-phase thin-layer chromatography plate in which a three-component dye mixture, viz., Fat Red 7B, Solvent Green 3, and Solvent Blue 35, was spotted and the components were separated. Development lanes were scanned by the sampling probe operated under computer control (x, y plane) while full-scan mass spectra were recorded using a quadrupole ion trap mass spectrometer. In addition, the ability to sample the surface of pharmaceutical tablets (viz., Extra Strength Tylenol(reg. sign) and Evista(reg. sign) tablets) and to detect the active ingredients (acetaminophen and raloxifene, respectively) selectively was demonstrated using tandem mass spectrometry (MS/MS). Finally, the capability to sample analyte solutions from the wells of a 384-well microtiter plate and to perform quantitative analyses using MS/MS detection was illustrated with cotinine standards spiked with cotinine-d{sub 3} as an internal standard.

  20. Ambient diode laser desorption dielectric barrier discharge ionization mass spectrometry of nonvolatile chemicals.

    Science.gov (United States)

    Gilbert-López, Bienvenida; Schilling, Michael; Ahlmann, Norman; Michels, Antje; Hayen, Heiko; Molina-Díaz, Antonio; García-Reyes, Juan F; Franzke, Joachim

    2013-03-19

    In this work, the combined use of desorption by a continuous wave near-infrared diode laser and ionization by a dielectric barrier discharge-based probe (laser desorption dielectric barrier discharge ionization mass spectrometry (LD-DBDI-MS)) is presented as an ambient ionization method for the mass spectrometric detection of nonvolatile chemicals on surfaces. A separation of desorption and ionization processes could be verified. The use of the diode laser is motivated by its low cost, ease of use, and small size. To achieve an efficient desorption, the glass substrates are coated at the back side with a black point (target point, where the sample is deposited) in order to absorb the energy offered by the diode laser radiation. Subsequent ionization is accomplished by a helium plasmajet generated in the dielectric barrier discharge source. Examples on the application of this approach are shown in both positive and negative ionization modes. A wide variety of multiclass species with low vapor pressure were tested including pesticides, pharmaceuticals and explosives (reserpine, roxithromycin, propazine, prochloraz, spinosad, ampicillin, dicloxacillin, enrofloxacin, tetracycline, oxytetracycline, erythromycin, spinosad, cyclo-1,3,5,7-tetramethylene tetranitrate (HMX), and cyclo-1,3,5-trimethylene trinitramine (RDX)). A comparative evaluation revealed that the use of the laser is advantageous, compared to just heating the substrate surface. PMID:23419061

  1. Cell Recovery after Combined Action of Ionizing Radiation and Chemicals

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jin Kyu; Roh, Chang Hyun; Ryu, Tae Ho [Korea Atomic Energy Research Institute, Jeongeup (Korea, Republic of); Komarova, Ludmila N.; Petin, Vladislav G. [Medical Radiological Research Center, Obninsk (Russian Federation)

    2012-05-15

    Damage repair in malignant cells would be problematic in sterilization of microorganisms and treatment of cancer, as well. The inhibition of cell recovery and DNA single and double strand breaks repair by chemicals is expressed both as a deceleration of recovery rate and a lesser extent of recovery. Three possibilities are involved in the inhibition of cell recovery: (1) impairment of the recovery process itself, (2) increased irreversible damage, and (3) simultaneous exert of the two. There have been fee publications regarding these problems. The aim of this study was to determine which of these points are involved in the inhibition of cell recovery. In this study, a quantitative approach describing cell recovery from potentially lethal damage as a decrease in the effective dose was used

  2. Identification of Perfluorooctanoic Acid Release from Commercial Coated Cooking Pans by Liquid Chromatography Coupled to Electrospray Ionization Tandem Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Monica Bononi

    2007-01-01

    Full Text Available Salts of perfluorooctanoic acid (PFOA can be used in the manufacture of fluoropolymers employed for coating pans; moreover, PFOA can be formed as a byproduct of thermolysis of the aforesaid fluoropolymers. This study was carried out to evaluate PFOA migration into food cooked in fluoropolymer-coated pans. The pans were purchased from a local retailer and subjected to cooking conditions. Used oil was extracted with a methanol/water solution and analyzed by liquid chromatography tandem mass spectrometry (LC/MS/MS. We found that PFOA can enter cooked food during a container's first phases of use, not only in containers already abused by kitchen tools or otherwise scratched.

  3. Determination of torasemide in human plasma and its bioequivalence study by high-performance liquid chromatography with electrospray ionization tandem mass spectrometry$

    Institute of Scientific and Technical Information of China (English)

    Lin Zhang; Rulin Wang; Yuan Tian; Zunjian Zhang

    2016-01-01

    A sensitive and selective method using high-performance liquid chromatography coupled with elec-trospray ionization tandem mass spectrometry (HPLC–ESI–MS) to determine the concentration of tor-asemide in human plasma samples was developed and validated. Tolbutamide was chosen as the internal standard (IS). The chromatography was performed on a Gl Sciences Inertsil ODS-3 column (100 mm ? 2.1 mm i.d., 5.0 mm) within 5 min, using methanol with 10 mM ammonium formate (60:40, v/v) as mobile phase at a flow rate of 0.2 mL/min. The targeted compound was detected in negative io-nization at m/z 347.00 for torasemide and 269.00 for IS. The linearity range of this method was found to be within the concentration range of 1–2500 ng/mL (r¼0.9984) for torasemide in human plasma. The accuracy of this measurement was between 94.05%and 103.86%. The extracted recovery efficiency was from 84.20% to 86.47% at three concentration levels. This method was also successfully applied in pharmacokinetics and bioequivalence studies in Chinese volunteers.

  4. Liquid Chromatography-electrospray Ionization Tandem Mass Spectrometry for Simultaneous Determination of Metformin and Glimepiride in Beagle Dog Plasma and Bioequivalence Study

    Institute of Scientific and Technical Information of China (English)

    BAI Jing; SHI Xiao-wei; DU Ying-feng; XIANG Bai; WANG Shuai; CAO De-ying

    2012-01-01

    A sensitive and selective liquid chromatography-electrospray ionization tandem mass spectrometry(LC-ESI-MS/MS) was used for the simultaneous determination of metformin and glimepiride in beagle dog plasma with glipizide as internal standard(IS).After simplified protein precipitation with methanol,both the analytes and IS were chromatographed on a Zorbax CN column via gradient elution with methanol(containing 5 mmol/L ammonium acetate) and 5 mmol/L aqueous ammonium acetate as the mobile phase.Detection was performed by multiple reaction monitoring(MRM) scanning via ESI source operated in positive ionization mode.Specificity,linearity,accuracy,precision,recovery,matrix effect and stability were validated for metformin and glimepiride in beagle dog plasma.The calibration curves were linear in a concentration range of 10--10000 ng/mL for metformin and 4--4000 ng/mL for glimepiride with both correlation coefficients higher than 0.99.The recoveries obtained for the analytes and IS were all between 82.7% and 101.2%.The method exhibited excellent performance in terms of selectivity,robustness,short analytical time and simplicity of sample preparation.Finally,the proposed method was applied to a bioequivalence study of self-made bilayer tablet and commercial formulation containing 500 mg of metformin and 1 mg of glimepiride in beagle dogs.

  5. Determination of torasemide in human plasma and its bioequivalence study by high-performance liquid chromatography with electrospray ionization tandem mass spectrometry

    Directory of Open Access Journals (Sweden)

    Lin Zhang

    2016-04-01

    Full Text Available A sensitive and selective method using high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (HPLC–ESI–MS to determine the concentration of torasemide in human plasma samples was developed and validated. Tolbutamide was chosen as the internal standard (IS. The chromatography was performed on a Gl Sciences Inertsil ODS-3 column (100 mm×2.1 mm i.d., 5.0 µm within 5 min, using methanol with 10 mM ammonium formate (60:40, v/v as mobile phase at a flow rate of 0.2 mL/min. The targeted compound was detected in negative ionization at m/z 347.00 for torasemide and 269.00 for IS. The linearity range of this method was found to be within the concentration range of 1–2500 ng/mL (r=0.9984 for torasemide in human plasma. The accuracy of this measurement was between 94.05% and 103.86%. The extracted recovery efficiency was from 84.20% to 86.47% at three concentration levels. This method was also successfully applied in pharmacokinetics and bioequivalence studies in Chinese volunteers.

  6. Ultra high performance liquid chromatography with electrospray ionization tandem mass spectrometry coupled with hierarchical cluster analysis to evaluate Wikstroemia indica (L.) C. A. Mey. from different geographical regions.

    Science.gov (United States)

    Wei, Lan; Wang, Xiaobo; Mu, Shanxue; Sun, Lixin; Yu, Zhiguo

    2015-06-01

    A sensitive, rapid and simple ultra high performance liquid chromatography with electrospray ionization tandem mass spectrometry method was developed to determine seven constituents (umbelliferone, apigenin, triumbelletin, daphnoretin, arctigenin, genkwanin and emodin) in Wikstroemia indica (L.) C. A. Mey. The chromatographic analysis was performed on an ACQUITY UPLC® BEH C18 column (2.1 × 50 mm, 1.7 μm) by gradient elution with the mobile phase of 0.05% formic acid aqueous solution (A) and acetonitrile (B). Multiple reaction monitoring mode with positive and negative electrospray ionization interface was carried out to detect the components. This method was validated in terms of specificity, linearity, accuracy, precision and stability. Excellent linear behavior was observed over the certain concentration ranges with the correlation coefficient values higher than 0.999. The intraday and innerday precisions were within 2.0%. The recoveries of seven analytes were 99.4-101.1% with relative standard deviation less than 1.2%. The 18 Wikstroemia indica samples from different origins were classified by hierarchical clustering analysis according to the contents of seven components. The results demonstrated that the developed method could successfully be used to quantify simultaneously of seven components in Wikstroemia indica and could be a helpful tool for the detection and confirmation of the quality of traditional Chinese medicines. PMID:25866087

  7. Analysis of triptophenolide and its related compounds from Tripterygium wilfordii Hook.f by electrospray ionization tandem mass spectrometry

    Science.gov (United States)

    Li, Rui; Peng, Aihua; He, Chunmei; Wang, Xianhuo; Shi, Jianyou; Chen, Lijuan; Wei, Yuquan

    2008-11-01

    Triptophenolide and its related compounds from Tripterygium wilfordii Hook.f is a kind of diterpenoids which shows anti-inflammatory activity. To study the metabolites of triptophenolide related compounds, the fragmentation mechanisms of them were investigated by using negative electrospray tandem mass spectrometry. With the aid of high resolution of ESI-QTOF-MS/MS, the fragmentation mechanisms of six diterpenoid compounds were systematically investigated. The fragmentation behavior mainly depends on what substituent groups the benzyl C ring bears. If there is a hydroxyl group on the position of C14, loss of CH4 is dominating. However, the successive loss of two CH3 radicals is predominant when the hydroxyl group of O14 is methylated. The lactone ring is prone to be dissociated to loss of CO, CO2 and C2H2O2 molecules. The pericyclic reaction can occur on A ring if there is an active hydrogen resides on C ring. Furthermore, one metabolite of compound A1 was confirmed by cytochrome P450 in vitro and the structure was proposed by tandem mass experiment together with the fragmentation mechanisms of this type of compounds.

  8. Atmospheric Pressure Chemical Ionization Sources Used in The Detection of Explosives by Ion Mobility Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Waltman, Melanie J. [New Mexico Inst. of Mining and Technology, Socorro, NM (United States)

    2010-05-01

    Explosives detection is a necessary and wide spread field of research. From large shipping containers to airline luggage, numerous items are tested for explosives every day. In the area of trace explosives detection, ion mobility spectrometry (IMS) is the technique employed most often because it is a quick, simple, and accurate way to test many items in a short amount of time. Detection by IMS is based on the difference in drift times of product ions through the drift region of an IMS instrument. The product ions are created when the explosive compounds, introduced to the instrument, are chemically ionized through interactions with the reactant ions. The identity of the reactant ions determines the outcomes of the ionization process. This research investigated the reactant ions created by various ionization sources and looked into ways to manipulate the chemistry occurring in the sources.

  9. Atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry for complex thiophenic mixture analysis

    KAUST Repository

    Hourani, Nadim

    2013-10-01

    Rationale Polycyclic aromatic sulfur heterocycles (PASHs) are detrimental species for refining processes in petroleum industry. Current mass spectrometric Methods that determine their composition are often preceded by derivatization and dopant addition approaches. Different ionization Methods have different impact on the molecular assignment of complex PASHs. The analysis of such species under atmospheric pressure chemical ionization (APCI) is still considered limited due to uncontrolled ion generation with low- and high-mass PASHs. Methods The ionization behavior of a model mixture of five selected PASH standards was investigated using an APCI source with nitrogen as the reagent gas. A complex thiophenic fraction was separated from a vacuum gas oil (VGO) and injected using the same method. The samples were analyzed using Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS). RESULTS PASH model analytes were successfully ionized and mainly [M + H]+ ions were produced. The same ionization pattern was observed for the real thiophenic sample. It was found that S1 class species were the major sulfur-containing species found in the VGO sample. These species indicated the presence of alkylated benzothiophenic (BT), dibenzothiophenic (DBT) and benzonaphthothiophenic (BNT) series that were detected by APCI-FTICR MS. CONCLUSIONS This study provides an established APCI-FTICR MS method for the analysis of complex PASHs. PASHs were detected without using any derivatization and without fragmentation. The method can be used for the analysis of S-containing crude oil samples. © 2013 John Wiley & Sons, Ltd.

  10. Secondary ionization of chemical warfare agent simulants: atmospheric pressure ion mobility time-of-flight mass spectrometry.

    Science.gov (United States)

    Steiner, Wes E; Clowers, Brian H; Haigh, Paul E; Hill, Herbert H

    2003-11-15

    For the first time, the use of a traditional ionization source for ion mobility spectrometry (radioactive nickel ((63)Ni) beta emission ionization) and three alternative ionization sources (electrospray ionization (ESI), secondary electrospray ionization (SESI), and electrical discharge (corona) ionization (CI)) were employed with an atmospheric pressure ion mobility orthogonal reflector time-of-flight mass spectrometer (IM(tof)MS) to detect chemical warfare agent (CWA) simulants from both aqueous- and gas-phase samples. For liquid-phase samples, ESI was used as the sample introduction and ionization method. For the secondary ionization (SESI, CI, and traditional (63)Ni ionization) of vapor-phase samples, two modes of sample volatilization (heated capillary and thermal desorption chamber) were investigated. Simulant reference materials, which closely mimic the characteristic chemical structures of CWA as defined and described by Schedule 1, 2, or 3 of the Chemical Warfare Convention treaty verification, were used in this study. A mixture of four G/V-type nerve simulants (dimethyl methylphosphonate, pinacolyl methylphosphonate, diethyl phosphoramidate, and 2-(butylamino)ethanethiol) and one S-type vesicant simulant (2-chloroethyl ethyl sulfide) were found in each case (sample ionization and introduction methods) to be clearly resolved using the IM(tof)MS method. In many cases, reduced mobility constants (K(o)) were determined for the first time. Ion mobility drift times, flight times, relative signal intensities, and fragmentation product signatures for each of the CWA simulants are reported for each of the methods investigated. PMID:14615983

  11. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry.

    Science.gov (United States)

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2016-07-01

    We propose detecting a fragment ion (Ph2As(+)) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH(+)) of DA, DC, DPAH, and BDPAO could produce Ph2As(+) through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As(+) signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH(+) signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As(+). Graphical Abstract ᅟ. PMID:27098411

  12. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry

    Science.gov (United States)

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2016-07-01

    We propose detecting a fragment ion (Ph2As+) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH+) of DA, DC, DPAH, and BDPAO could produce Ph2As+ through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As+ signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH+ signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As+.

  13. Comparison of electrospray ionization, atmospheric pressure chemical ionization and atmospheric pressure photoionization for a lipidomic analysis of Leishmania donovani.

    Science.gov (United States)

    Imbert, Laurent; Gaudin, Mathieu; Libong, Danielle; Touboul, David; Abreu, Sonia; Loiseau, Philippe M; Laprévote, Olivier; Chaminade, Pierre

    2012-06-15

    A comparison of electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) for the analysis of a wide range of lipids has been performed on standard mixtures and extracts of Leishmania donovani promastigotes resistant to Amphotericin B (AmB). Calibration model, precision, limits of detection and quantification (LOD and LOQ) were assessed for each source. APPI provided the highest signal, signal-to-noise (S/N), and sensitivity for non-polar and low-polarity lipids, while ESI and APCI gave better results for the most polar ones. The linear model was valid for all lipids, except for one class with APPI, six classes with ESI, and eleven classes with APCI. LODs ranged from 0.2 to 20 μg mL(-1) for ESI, from 0.1 to 10 μg mL(-1) for APCI, and from 0.02 to 9.5 μg mL(-1) for APPI. LOQs ranged from 0.2 to 61 μg mL(-1) for ESI, from 0.4 to 31 μg mL(-1) for APCI, and from 0.1 to 29 μg mL(-1) for APPI. Each source provided similar lipid composition and variations in a comparison of three different L. donovani samples: miltefosine-treated, miltefosine-resistant and treated miltefosine-resistant parasites. A treated miltefosine-resistant sample was finally analyzed with each ion source in order to verify that the same lipid molecular species are detected. PMID:22560453

  14. Influence of soil pH on the sorption of ionizable chemicals

    DEFF Research Database (Denmark)

    Franco, Antonio; Fu, Wenjing; Trapp, Stefan

    2009-01-01

    The soil-water distribution coefficient of ionizable chemicals (K-d) depends on the soil acidity, mainly because the pH governs speciation. Using pH-specific K-d values normalized to organic carbon (K-OC) from the literature, a method was developed to estimate the K-OC of monovalent organic acids...... and bases. The regression considers pH-dependent speciation and species-specific partition coefficients, calculated from the dissociation constant (pK(a)) and the octanol-water partition coefficient of the neutral molecule (log P-n). Probably because of the lower pH near the organic colloid-water...... impact of pH on the total sorption is contrasting. In fact, the shortcomings of the model assumptions affect the predictive power for acids and for bases differently. We evaluated accuracy and limitations of the regressions for their use in the environmental fate assessment of ionizable chemicals....

  15. Dependences of Ratio of the Luminosity to Ionization on Velocity and Chemical Composition of Meteors

    Science.gov (United States)

    Narziev, M.

    2011-01-01

    On the bases of results simultaneous photographic and radio echo observations, the results complex radar and television observations of meteors and also results of laboratory modeling of processes of a luminescence and ionization, correlation between of luminous intensity Ip to linear electronic density q from of velocities and chemical structure are investigated. It is received that by increasing value of velocities of meteors and decrease of nuclear weight of substance of particles, lg Ip/q decreased more than one order.

  16. Real-time monitoring of volatile organic compounds using chemical ionization mass spectrometry

    Science.gov (United States)

    Mowry, Curtis Dale; Thornberg, Steven Michael

    1999-01-01

    A system for on-line quantitative monitoring of volatile organic compounds (VOCs) includes pressure reduction means for carrying a gaseous sample from a first location to a measuring input location maintained at a low pressure, the system utilizing active feedback to keep both the vapor flow and pressure to a chemical ionization mode mass spectrometer constant. A multiple input manifold for VOC and gas distribution permits a combination of calibration gases or samples to be applied to the spectrometer.

  17. Analysis of insect triacylglycerols using liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry

    Czech Academy of Sciences Publication Activity Database

    Kofroňová, Edita; Cvačka, Josef; Jiroš, Pavel; Sýkora, D.; Valterová, Irena

    2009-01-01

    Roč. 111, č. 5 (2009), s. 519-525. ISSN 1438-7697 R&D Projects: GA AV ČR IAA4055403; GA MŠk 2B06007 Institutional research plan: CEZ:AV0Z40550506 Keywords : atmospheric pressure chemical ionization * bumblebees * fat body * NARP-HPLC Subject RIV: CC - Organic Chemistry Impact factor: 1.831, year: 2009

  18. Mutagenic effect of ionizing radiation and chemical and environmental agents in Tradescantia

    International Nuclear Information System (INIS)

    The studies covered the following problems: an influence of some environmental agents on the mutagenic effectiveness of ionizing radiation, interaction between ionizing radiation and chemical mutagens in the induction of somatic mutations and also an application of Tradescantia model system for biological monitoring. The studies showed that the pretreatment of Tradescantia plants with sodium fluoride or the modification of the soil composition with dolomite admixture, visibly influences plants radiosensitivity. The analysis of the changes in the dose-response curves suggested that the employed agents were influencing in different ways the repair processes of the DNA. The studies on the interaction between agents proved that the synergistic effect occurs in case of combined action of ionizing radiation with such chemical mutagens as ethyl methansulfonate or 1,2 dibromomethane. It was also discovered that in the range of low doses the effect was proportional to radiation dose and total exposition to chemical mutagen. The field application of Tradescantia method defined the mutagenicity of air pollution in the Cracow area. The highest frequencies of mutations were detected after the Chernobyl accident and after the damage of the filters in the Pharmaceutical Plant. The applied method was evaluated in respect of its usefulness for biological monitoring of environmental pollution. 163 refs. (author)

  19. Performing protein crosslinking using gas-phase cleavable chemical crosslinkers and liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Argo, Andrew S; Shi, Chunxiao; Liu, Fan; Goshe, Michael B

    2015-11-01

    In this article, we describe our methods and protocols using collision-induced dissociative chemical crosslinking-tandem mass spectrometry (CID-CXL-MS/MS) analysis and the practical considerations when implementing these reagents and methodology for protein crosslinking studies. The synthesis of our novel chemical crosslinkers is described as well as their use for effectively labeling protein and protein complexes. Several sample preparation methods for liquid chromatography-tandem mass spectrometry are provided including the enrichment of interpeptide crosslinks. For identification of CID-CXL-MS/MS crosslinks, details regarding MS acquisition parameters and the utilization of various mass spectrometers are addressed along with post-data acquisition analysis to identify interpeptide crosslinks. Once the CID-CXL-MS/MS approach is optimized for a protein target or a set of targets, it can be used as a tool for biological research for studying protein structure when integrated with data obtained using other techniques, such as NMR, X-ray crystallography, and cryo-electron microscopy, or extended to the study of protein-protein interactions in physiological environments. PMID:26091612

  20. Mutation research with ionizing radiations and chemicals using drosophila: problems, results and perspectives

    International Nuclear Information System (INIS)

    The results of mutagenesis studies with Drosophila are examined in order to inquire the extent to which the genetic responses to ionizing radiations and to chemical mutagens share common features, to identify those findings that may have validity beyond the confines of this species, and to assess the contributions and implications of Drosophila results to the problems of mutagenicity testing and of the evaluation of genetic hazards to man from exposure to environmental chemicals. The results obtained in the studies permit the estimation of X-irradiation equivalent doses of EMS for the induction of sex-linked recessive lethals and specific locus mutations in mature spermatozoa. (Auth.)

  1. Modelling the Fate of Ionizable Trace Organic Chemicals from Consumption to Food Crops

    DEFF Research Database (Denmark)

    Polesel, Fabio; Plósz, Benedek G.; Trapp, Stefan

    In this study, we developed and applied a simulation tool to comprehensively predict the fate of three ionizable trace chemicals (triclosan—TCS, furosemide—FUR, ciprofloxacin—CIP) from human consumption/excretion up to the accumulation in wheat, following application of sewage sludge or irrigation...... with river water. Highest translocation to wheat (4.3 μg kgDW-1 in grain) was calculated for FUR, being more significant with irrigation (>45% of emission to soil) than with sludge application (<30%). The simulation tool presented here can be used for estimating human exposure to trace chemicals via...

  2. Studies on Fragmentation Pathways of N-Ethoxy(phenyl) phosphoryl Amino Acids by Electrospray Ionization Tandem Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The positive and negative ESI-MS/MS spectra of N-ethoxy(phenyl) phosphoryl amino acids(EPP-AA) were investigated by electrospray ionization(ESI) ion trap mass spectrometry. The fragmentation pathways of [M + Na]+ and [M-H]- ions areproposed and rationalized. The observation may have some potential applications in the interpretation of the MS/MS spectra of novel N-phosphoryl compounds. The complexity of MS/MS spectra of EPP-AA [M + Na] + ions is decreased compared with that of N-dialkyloxyphosphoryl amino acid. Therefore, the new phosphonamidate method may be considered one of the superior methods that can be used in sequencing peptides and proteins extensively.

  3. Study of matrix effects for liquid chromatography-electrospray ionization tandem mass spectrometric analysis of 4 aminoglycosides residues in milk.

    Science.gov (United States)

    Wang, Yuan; Li, Shaohui; Zhang, Feifang; Lu, Yifeng; Yang, Bingcheng; Zhang, Feng; Liang, Xinmiao

    2016-03-11

    Matrix effect (ME) is always a major issue for the development of LC-MS/MS method. ME resulting from co-eluting residual matrix components can affect the ionization efficiency of target analytes, leading to quantification errors of the analytes of interest. The present work evaluates MEs of milk samples on simultaneous analysis of four aminoglycosides residues via LC-ESI/MS/MS including streptomycin, dihydrostreptomycin, spectinomycin and kanamycin. Approaches to reduce MEs were examined: optimization of the sample preparation, sample dilution and lower flow rate used. Three commercial sorbents were tested including Oasis MCX, Oasis HLB and Oasis WCX. WCX behaved better for all analytes, but high MEs (80.8-134.9%) were obtained. Therefore, a consecutive SPE of tC18-WCX was found to effectively reduce ME. Milk samples from different manufacturers were analyzed and low MEs (85.6-112.9%) were obtained. PMID:26875117

  4. Gas phase studies on terpenes by ion mobility spectrometry using different atmospheric pressure chemical ionization techniques

    Science.gov (United States)

    Borsdorf, H.; Stone, J. A.; Eiceman, G. A.

    2005-11-01

    The ionization pathways and drift behavior were determined for sets of constitutional isomeric and stereoisomeric non-polar hydrocarbons (unsaturated monocyclic terpenes, unsaturated and saturated bicyclic terpenes) using ion mobility spectrometry (IMS) with different techniques of atmospheric pressure chemical ionization (APCI) to assess how structural and stereochemical differences influence ion formation. Depending on the structural features, different ions were observed for constitutional isomers using ion mobility spectrometry with photoionization (PI) and corona discharge (CD) ionization. Photoionization provides ion mobility spectra containing one major peak for saturated compounds while at two peaks were observed for unsaturated compounds, which can be assigned to product ions related to monomer and dimer ions. However, differences in relative abundance of product ions were found depending on the position of the double bond. Although IMS using corona discharge ionization permits the most sensitive detection of non-polar hydrocarbons, the spectra are complex and differ from those obtained using photoionization. Additional cluster ions and fragment ions were detected. Only small differences in ion mobility spectra were observed for the diastereomers while the enantiomers provide identical spectra. The structure of the product ions formed was checked by investigations using the coupling of ion mobility spectrometry with mass spectrometry (IMS-MS).

  5. Study on Flavonoids From Meconopsis Maxim by Electrospray Ionization Tandem Mass Spectrometry%绿绒蒿属植物中黄酮类化合物的电喷雾电离串联质谱研究

    Institute of Scientific and Technical Information of China (English)

    阿布拉江·克依木; 尚小雅; 贺玖明; 再帕尔·阿不力孜; 石建功

    2004-01-01

    The fragmentation behavior of six known flavonoids from Meconopsis Maxim were studied by electrospray ionization tandem mass spectrometry (ESI-MSn). Besides the structure of aglycones and hydroxyl group on it, the position of the sugar substitution also affected the fragmentation of the flavonoids. The diagnostic fragmentations of flavonoids and aglycones were obtained in the positive and negative ion ESI-MSn experiments, and the fragmentation pathways were discussed.

  6. Differential Isotope Labeling of 38 Dietary Polyphenols and Their Quantification in Urine by Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometry.

    Science.gov (United States)

    Achaintre, David; Buleté, Audrey; Cren-Olivé, Cécile; Li, Liang; Rinaldi, Sabina; Scalbert, Augustin

    2016-03-01

    A large number of polyphenols are consumed with the diet and may contribute to the prevention of chronic diseases such as cardiovascular diseases, diabetes, cancers, and neurodegenerative diseases. More comprehensive methods are needed to measure exposure to this complex family of bioactive plant compounds in epidemiological studies. We report here a novel method enabling the simultaneous measurement in urine of 38 polyphenols representative of the main classes and subclasses found in the diet. This method is based on differential (12)C-/(13)C-isotope labeling of polyphenols through derivatization with isotopic dansyl chloride reagents and on the analysis of the labeled polyphenols by tandem mass spectrometry. This derivatization approach overcomes the need for costly labeled standards. Different conditions for enzyme hydrolysis of polyphenol glucuronides and sulfate esters, extraction, and dansylation of unconjugated aglycones were tested and optimized. Limits of quantification varied from 0.01 to 1.1 μM depending on polyphenols. Intrabatch coefficients of variation varied between 3.9% and 9.6%. Interbatch variations were lower than 15% for 31 compounds and lower than 29% for 6 additional polyphenols out of the 38 tested. Thirty seven polyphenols were validated and then analyzed in 475, 24 h urine samples from the European Prospective Investigation on Cancer and Nutrition (EPIC) study. Thirty four polyphenols could be detected and successfully estimated and showed large interindividual variations of concentrations (2-3 orders of magnitude depending on the compound), with median concentrations spanning from 0.01 to over 1000 μM for all 34 compounds. PMID:26814424

  7. Determination of Phenolic Content in Different Barley Varieties and Corresponding Malts by Liquid Chromatography-diode Array Detection-Electrospray Ionization Tandem Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Daniel O. Carvalho

    2015-08-01

    Full Text Available A simple and reliable method for the simultaneous determination of nine phenolic compounds in barley and malted barley was established, using liquid chromatography-diode array detection-electrospray ionization tandem mass spectrometry (HPLC-DAD-ESI-MS/MS. The phenolic compounds can be easily detected with both systems, despite significant differences in sensitivity. Concentrations approximately 180-fold lower could be achieved by mass spectrometry analysis compared to diode array detection, especially for the flavan-3-ols (+-catechin and (−-epicatechin, which have poor absorptivity in the UV region. Malt samples were characterized by higher phenolic content comparing to corresponding barley varieties, revealing a significant increase of the levels of (+-catechin and (−-epicatechin during the malting process. Moreover, the industrial malting is responsible for modification on the phenolic profile from barley to malt, namely on the synthesis or release of sinapinic acid and epicatechin. Accordingly, the selection of the malting parameters, as well as the barley variety plays an important role when considering the quality and antioxidant stability of beer.

  8. Selective and rapid determination of raltegravir in human plasma by liquid chromatography–tandem mass spectrometry in the negative ionization mode

    Directory of Open Access Journals (Sweden)

    Ajay Gupta

    2015-04-01

    Full Text Available A selective and rapid high-performance liquid chromatography–tandem mass spectrometry method was developed and validated for the quantification of raltegravir using raltegravir-d3 as an internal standard (IS. The analyte and IS were extracted with methylene chloride and n-hexane solvent mixture from 100 µL human plasma. The chromatographic separation was achieved on a Chromolith RP-18e endcapped C18 (100 mm×4.6 mm column in a run time of 2.0 min. Quantitation was performed in the negative ionization mode using the transitions of m/z 443.1→316.1 for raltegravir and m/z 446.1→319.0 for IS. The linearity of the method was established in the concentration range of 2.0–6000 ng/mL. The mean extraction recovery for raltegravir and IS was 92.6% and 91.8%, respectively, and the IS-normalized matrix factors for raltegravir ranged from 0.992 to 0.999. The application of this method was demonstrated by a bioequivalence study on 18 healthy subjects.

  9. Investigation of natural phosphatidylcholine sources: separation and identification by liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS2) of molecular species.

    Science.gov (United States)

    Le Grandois, Julie; Marchioni, Eric; Zhao, Minjie; Giuffrida, Francesca; Ennahar, Saïd; Bindler, Françoise

    2009-07-22

    This study is a contribution to the exploration of natural phospholipid (PL) sources rich in long-chain polyunsaturated fatty acids (LC-PUFAs) with nutritional interest. Phosphatidylcholines (PCs) were purified from total lipid extracts of different food matrices, and their molecular species were separated and identified by liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS(2)). Fragmentation of lithiated adducts allowed for the identification of fatty acids linked to the glycerol backbone. Soy PC was particularly rich in species containing essential fatty acids, such as (18:2-18:2)PC (34.0%), (16:0-18:2)PC (20.8%), and (18:1-18:2)PC (16.3%). PC from animal sources (ox liver and egg yolk) contained major molecular species, such as (16:0-18:2)PC, (16:0-18:1)PC, (18:0-18:2)PC, or (18:0-18:1)PC. Finally, marine source (krill oil), which was particularly rich in (16:0-20:5)PC and (16:0-22:6)PC, appeared to be an interesting potential source for food supplementation with LC-PUFA-PLs, particularly eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). PMID:19545117

  10. Determination of selected antibiotics in the Victoria Harbour and the Pearl River, South China using high-performance liquid chromatography-electrospray ionization tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Xu Weihai [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, Guangzhou 510640 (China); School of Chemistry and Chemical Engineering, Zhongshan University, Guangzhou 510250 (China); Department of Civil and Structural Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (China); Post-graduate School of the Chinese Academy of Sciences, Beijing 100039 (China); Zhang Gan [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, Guangzhou 510640 (China)]. E-mail: zhanggan@gig.ac.cn; Zou Shichun [School of Chemistry and Chemical Engineering, Zhongshan University, Guangzhou 510250 (China); Li Xiangdong [Department of Civil and Structural Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (China); Liu Yuchun [School of Chemistry and Chemical Engineering, Zhongshan University, Guangzhou 510250 (China)

    2007-02-15

    Nine selected antibiotics in the Victoria Harbour of Hong Kong and the Pearl River at Guangzhou, South China, were analyzed using high-performance liquid chromatography-electrospray ionization tandem mass spectrometry. The results showed that the concentrations of antibiotics were mainly below the limit of quantification (LOQ) in the marine water of Victoria Harbour. However, except for amoxicillin, all of the antibiotics were detected in the Pearl River during high and low water seasons with the median concentrations ranging from 11 to 67 ng/L, and from 66 to 460 ng/L, respectively; and the concentrations in early spring were about 2-15 times higher than that in summer with clearer diurnal variations. It was suggested that the concentrations of antibiotics in the high water season were more affected by wastewater production cycles due to quick refreshing rate, while those in the low water season may be more sensitive to the water column dynamics controlled by tidal processes in the river. - Antibiotics were found at high concentrations in an urban reach of Pearl River in southern China with contrast diurnal variations between the high and low water seasons.

  11. Determination of selected antibiotics in the Victoria Harbour and the Pearl River, South China using high-performance liquid chromatography-electrospray ionization tandem mass spectrometry

    International Nuclear Information System (INIS)

    Nine selected antibiotics in the Victoria Harbour of Hong Kong and the Pearl River at Guangzhou, South China, were analyzed using high-performance liquid chromatography-electrospray ionization tandem mass spectrometry. The results showed that the concentrations of antibiotics were mainly below the limit of quantification (LOQ) in the marine water of Victoria Harbour. However, except for amoxicillin, all of the antibiotics were detected in the Pearl River during high and low water seasons with the median concentrations ranging from 11 to 67 ng/L, and from 66 to 460 ng/L, respectively; and the concentrations in early spring were about 2-15 times higher than that in summer with clearer diurnal variations. It was suggested that the concentrations of antibiotics in the high water season were more affected by wastewater production cycles due to quick refreshing rate, while those in the low water season may be more sensitive to the water column dynamics controlled by tidal processes in the river. - Antibiotics were found at high concentrations in an urban reach of Pearl River in southern China with contrast diurnal variations between the high and low water seasons

  12. Analysis by liquid chromatography-electrospray ionization tandem mass spectrometry and acute toxicity evaluation for beta-blockers and lipid-regulating agents in wastewater samples.

    Science.gov (United States)

    Hernando, M D; Petrovic, M; Fernández-Alba, A R; Barceló, D

    2004-08-13

    This paper describes a multiresidue method for the extraction and determination of two therapeutic groups of pharmaceuticals, lipid-regulating agents (clofibric acid, bezafibrate, gemfibrocil, fenofibrate) and beta-blockers (atenolol, sotalol, metoprolol, betaxolol) in waters by solid-phase extraction followed by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS). Recoveries obtained from spiked HPLC water, as well as, from spiked real samples (sewage treatment plants influent and effluents, river and tap water) were all above 60%, with the exception of betaxolol with a 52% recovery. The quantitative MS analysis was performed using a multiple reaction monitoring. The LC-MS-MS method gave detection limits ranging from 0.017 to 1.25 microg/l in spiked effluent. Precision of the method, calculated as relative standard deviation, ranged from 3.7 to 18.5%. Individual and combined effects on Daphnia magna were evaluated for both therapeutic groups. Individual effects in culture medium showed these compounds as not harmful and not toxic, an exception is fenofibrate that was found to be harmful, but at high, in the environment unrealistic concentrations (EC50 of 50 mg/l). Combined effect in wastewater showed synergistic toxic effects at low concentration level (2 microg/l). PMID:15387181

  13. Determination of betamethasone and betamethasone 17-monopropionate in human plasma by liquid chromatography-positive/negative electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Zou, Jian-Jun; Dai, Li; Ding, Li; Xiao, Da-Wei; Bin, Zhu-Yu; Fan, Hong-Wei; Liu, Li; Wang, Guang-Ji

    2008-10-01

    This study presents a high-performance liquid chromatography-positive/negative electrospray ionization tandem mass spectrometric (LC-ESI(+/-)-MS-MS) method for the determination of betamethasone (BOH) and betamethasone 17-monopropionate (B17P) in human plasma using beclomethasone dipropionate as the internal standard (I.S.). Both compounds were extracted from human plasma with ether-cyclohexane (4:1, v/v) and were separated by HPLC on a Hanbon Lichrospher C(18) column with a mobile phase of methanol-water (85:15, v/v) at a flow rate of 0.7ml/min. Calibration curves were linear over the range of 0.10-50ng/ml for BOH and 0.050-50ng/ml for B17P. The inter-run relative standard deviations were less than 14.4% for BOH and 12.3% for B17P. The intra-run relative standard deviations were less than 9.3% for BOH and 7.9% for B17P. The mean plasma extraction recovery for BOH and B17P were in the ranges of 82.7-85.9% and 83.6-85.3%, respectively. The method was successfully applied to study the pharmacokinetics of a new formulation of betamethasone phosphate/betamethasone dipropionate injection in healthy Chinese volunteers. PMID:18757252

  14. Direct identification of phenolic constituents in Boldo Folium (Peumus boldus Mol.) infusions by high-performance liquid chromatography with diode array detection and electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Simirgiotis, M J; Schmeda-Hirschmann, G

    2010-01-22

    A very simple and direct method was developed for the qualitative analysis of polyphenols in boldo (Peumus boldus Mol., Monimiaceae) leaves infusions by high-performance liquid chromatography with diode array detection (HPLC-DAD) and electrospray ionization tandem mass spectrometry (HPLC-MS(n)). The phenolic constituents identified in infusions of the crude drug Boldo Folium were mainly proanthocyanidins and flavonol glycosides. In the infusions, 41 compounds were detected in male and 43 compounds in female leaf samples, respectively. Nine quercetin glycosides, eight kaempferol derivatives, nine isorhamnetin glycosides, three phenolic acids, one caffeoylquinic acid glycoside and twenty one proanthocyanidins were identified by HPLC-DAD and ESI-MS for the first time in the crude drug. Isorhamnetin glucosyl-di-rhamnoside was the most abundant flavonol glycoside in the male boldo sample, whereas isorhamnetin di-glucosyl-di-rhamnoside was the main phenolic compound in female boldo leaves infusion. The results suggest that the medicinal properties reported for this popular infusion should be attributed not only to the presence of catechin and boldine but also to several phenolic compounds with known antioxidant activity. The HPLC fingerprint obtained can be useful in the authentication of the crude drug Boldo Folium as well as for qualitative analysis and differentiation of plant populations in the tree distribution range. PMID:20022332

  15. Simultaneous determination of 13 quinolones in eggs using column high-performance liquid chromatography/electrospray ionization-tandem mass spectrometry and depletion of pefloxacin methanesulfonate in eggs.

    Science.gov (United States)

    Shen, Jianzhong; Li, Haiyan; Jiang, Haiyang; Zhou, Degang; Xu, Fei; Li, Jiancheng; Ding, Shuangyang

    2008-01-01

    An efficient method was developed for simultaneous determination of 13 quinolones--namely, enoaxacin (ENO), marbofloxacin (MAR), ciprofloxacin (CIP), norfloxacin (NOR), ofloxacin (OFL), pefloxacin methanesulfonate (PEF), danofloxacin (DAN), enrofloxacin (ENR), lomefloxacin (LOM), difloxacin (DIF), sarafloxacin (SAR), oxolinic acid (OXO), and flumequine (FLU)--in eggs by column liquid chromatography/electrospray ionization-tandem mass spectrometry. Samples were extracted with a phosphoric acid-phosphate buffer followed by purification with a solid-phase extraction cartridge. Recoveries for the 13 quinolones were 67-93% with intraday and interday coefficients of variation ranging from 4 to 9% and 2 to 18%, respectively. The limit of determination was 0.05 microg/kg for OXO and FLU; 0.1 microg/kg for MAR, OFL, CIP, LOM, DAN, SAR, DIF, NOR, and ENR; and 0.2 microg/kg for ENO and PEF. The method was also applied to study the depletion of PEF in eggs. The concentration of PEF increased and reached a maximum value on the third day, and then decreased rapidly until it could not be detected on day 32; its metabolite NOR was detectable on the second day, and then reached a maximum on the sixth day, after which it could not be detected until day 15. PMID:19202815

  16. Simultaneous Determination of Eight Ginsenosides in Rat Plasma by Liquid Chromatography-Electrospray Ionization Tandem Mass Spectrometry: Application to Their Pharmacokinetics.

    Science.gov (United States)

    Ma, Li-Yuan; Zhang, You-Bo; Zhou, Qi-Le; Yang, Yan-Fang; Yang, Xiu-Wei

    2015-01-01

    A high-performance liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) method was successfully developed and validated for the identification and determination of eight ginsenosides: ginsenoside Rg₁ (1); 20(S)-ginsenoside Rh₁ (2); 20(S)-ginsenoside Rg₂ (3); 20(R)-ginsenoside Rh₁ (4); 20(R)-ginsenoside Rg₂ (5); ginsenoside Rd (6); 20(S)-ginsenoside Rg₃ (7); and 20(R)-ginsenoside Rg₃ (8) in rat plasma. The established rapid method had high linearity, selectivity, sensitivity, accuracy, and precision. The method has been used successfully to study the pharmacokinetics of abovementioned eight ginsenosides for the first time. After an oral administration of total saponins in the stems-leaves of Panax ginseng C. A. Meyer (GTSSL) at a dose of 400 mg/kg, the ginsenosides 6, 7, and 8, belonging to protopanaxadiol-type saponins, exhibited relatively long tmax values, suggesting that they were slowly absorbed, while the ginsenosides 1-5, belonging to protopanaxatriol-type saponins, had different tmax values, which should be due to their differences in the substituted groups. Compounds 2 and 4, 3 and 5, 7 and 8 were three pairs of R/S epimerics at C-20, which was interesting that the t1/2 of 20(S)-epimers were always longer than those of 20(R)-epimers. This pharmacokinetic identification of multiple ginsenosides of GTSSL in rat plasma provides a significant basis for better understanding the clinical application of GTSSL. PMID:26633350

  17. Targeted analysis and determination of β-agonists, hormones, glucocorticoid and psychiatric drugs in feed by liquid chromatography with electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Zhu, Yufei; Xie, Shuyu; Chen, Dongmei; Pan, Yuanhu; Qu, Wei; Wang, Xu; Liu, Zhenli; Peng, Dapeng; Huang, Lingli; Tao, Yanfei; Yuan, Zonghui

    2016-07-01

    A comprehensive strategy combining a quantitative method was developed for 30 banned drugs including β-agonists, hormones, glucocorticoid and psychiatric drugs in swine and chicken feeds. This rapid, simple and effective extraction method was based on matrix solid-phase dispersion and electrospray ionization tandem mass spectrometry. The quantitative method was validated after previous statistical optimization of the main parameters of matrix solid-phase dispersion. The limit of quantification of dopamine hydrochloride, chlormadinone acetate, melengestrol acetate, testosterone propionate, nandrolone and midazolam was 2 μg/kg and that of the other 24 drugs was 1 μg/kg. The recoveries of β-agonists, hormones, glucocorticoid and psychiatric drugs spiked in swine and chicken feeds at a concentration range of 1-8 μg/kg were above 70.1% with inter-day relative standard deviations less than 15.8%. The analytical strategy was applied to 100 feed samples collected from a local market in Wuhan (China). Clenbuterol, ractopamine and melengestrol acetate were identified and quantified at the level 0.2∼3.5 μg/kg. The rapid and reliable method can be used to efficiently separate, characterize and quantify the residues of 30 banned drugs in swine and chicken feeds with advantages of simple pretreatment and environmental friendly nature. PMID:27145483

  18. Simultaneous determination of urinary parabens, bisphenol A, triclosan, and 8-hydroxy-2'-deoxyguanosine by liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Ren, Lu; Fang, Jianzhang; Liu, Guihua; Zhang, Jianqing; Zhu, Zhou; Liu, Honghe; Lin, Kai; Zhang, Huimin; Lu, Shaoyou

    2016-04-01

    A simple and fast method was developed for the simultaneous determination of five parabens, bisphenol A (BPA), triclosan (TCS), and 8-hydroxy-2'-deoxyguanosine (8-OHdG) in human urine using liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The solid-phase extraction (SPE) procedure, chromatographic conditions, and MS/MS parameters were optimized to achieve maximum sensitivity and accuracy for the analytes. The validation results showed that the correlation coefficients (R (2)) and recoveries ranged from 0.999 to 1 and 83.9 to 109.9 %, respectively, and the intra-day and inter-day precisions (relative standard deviation, RSD) were within the range of 1.3-8.5 % and 1.3-9.0 %, respectively. The limits of detection for the analytes ranged from 0.001 to 0.05 μg/L. The method was successfully employed to determine parabens, BPA, TCS, and 8-OHdG in urine samples from school students in Guangzhou, China. The results showed that methyl, ethyl, n-propyl parabens, BPA, TCS, and 8-OHdG were frequently detected in urine samples. n-Butyl and benzyl parabens were only detected in a part of the samples due to their low concentrations in urine. PMID:26873198

  19. Selective and rapid determination of raltegravir in human plasma by liquid chromatography-tandem mass spectrometry in the negative ionization mode

    Institute of Scientific and Technical Information of China (English)

    Ajay Gupta; Swati Guttikar; Priyanka A. Shah; Gajendra Solanki; Pranav S. Shrivastav; Mallika Sanyal

    2015-01-01

    A selective and rapid high-performance liquid chromatography–tandem mass spectrometry method was developed and validated for the quantification of raltegravir using raltegravir-d3 as an internal standard (IS). The analyte and IS were extracted with methylene chloride and n-hexane solvent mixture from 100 mL human plasma. The chromatographic separation was achieved on a Chromolith RP-18e endcapped C18 (100 mm ? 4.6 mm) column in a run time of 2.0 min. Quantitation was performed in the negative ionization mode using the transitions of m/z 443.1-316.1 for raltegravir and m/z 446.1-319.0 for IS. The linearity of the method was established in the concentration range of 2.0–6000 ng/mL. The mean extraction recovery for raltegravir and IS was 92.6% and 91.8%, respectively, and the IS-normalized matrix factors for raltegravir ranged from 0.992 to 0.999. The application of this method was demonstrated by a bioequivalence study on 18 healthy subjects.

  20. Identification of glycerophospholipid molecular species of mussel (Mytilus edulis) lipids by high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry.

    Science.gov (United States)

    Yin, Fa-Wen; Zhou, Da-Yong; Zhao, Qi; Liu, Zhong-Yuan; Hu, Xiao-Pei; Liu, Yan-Fei; Song, Liang; Zhou, Xin; Qin, Lei; Zhu, Bei-Wei; Shahidi, Fereidoon

    2016-12-15

    This study was carried out to identify the glycerophosphocholine (GPCho), glycerophosphoethanolamine (GPEtn) and glycerophosphoserine (GPSer) compositions in lipids extracted from mussels using Folch, Bligh-Dyer and methyl-tert-butyl ether (MTBE) methods by high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS). The molecular species of GPCho, GPEtn and GPSer were characterized according to the MS and MS/MS information. A semi-quantitative method using internal standard was established to compare the difference in glycerophospholipids (GP) between samples recovered with different methods. At least 212, 230 and 206 GP species were identified, respectively, from lipids recovered by Folch, Bligh-Dyer and MTBE methods. Most of the abundant GP species in mussels contained EPA and DHA. Some GP species with low content were not present in lipids recovered by the Folch and MTBE methods when compared with that recovered by the Bligh-Dyer method. However, for most GP species in lipids recovered by different methods, no quantitative differences existed. PMID:27451190

  1. Gas chromatography-microchip atmospheric pressure chemical ionization-mass spectrometry.

    Science.gov (United States)

    Ostman, Pekka; Luosujärvi, Laura; Haapala, Markus; Grigoras, Kestas; Ketola, Raimo A; Kotiaho, Tapio; Franssila, Sami; Kostiainen, Risto

    2006-05-01

    An atmospheric pressure chemical ionization (APCI) microchip is presented for combining a gas chromatograph (GC) to a mass spectrometer (MS). The chip includes capillary insertion channel, stopper, vaporizer channel, nozzle and nebulizer gas inlet fabricated on the silicon wafer, and a platinum heater sputtered on a glass wafer. These two wafers are joined by anodic bonding creating a two-dimensional version of an APCI microchip. The sample from GC is directed via heated transfer line capillary to the vaporizer channel of the APCI chip. The etched nozzle forms narrow sample plume, which is ionized by an external corona discharge needle, and the ions are analyzed by a mass spectrometer. The GC-microchip APCI-MS combination provides an efficient method for qualitative and quantitative analysis. The spectra produced by microchip APCI show intensive protonated molecule and some fragmentation products as in classical chemical ionization for structure elucidation. In quantitative analysis the GC-microchip APCI-MS showed good linearity (r(2) = 0.9989) and repeatability (relative standard deviation 4.4%). The limits of detection with signal-to-noise ratio of three were between 0.5 and 2 micromol/L with MS mode using selected ion monitoring and 0.05 micromol/L with MS/MS using multiple reaction monitoring. PMID:16642989

  2. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization

    Science.gov (United States)

    Vaikkinen, Anu; Kauppila, Tiina J.; Kostiainen, Risto

    2016-04-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M+. decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques.

  3. Direct Measurement of Atmospheric Ammonia from an Airborne Miniature Chemical Ionization Mass Spectrometer (miniCIMS)

    Science.gov (United States)

    Casados, K.; Schill, S.; Freeman, S.; Zoerb, M.; Bertram, T. H.; Lefer, B. L.

    2015-12-01

    Ammonia is emitted into the atmosphere from a variety of sources such as trees, ocean, diary fields, biomass burning, and fuel emissions. Previous studies have investigated the environmental impacts of atmospheric ammonia which can include chemical reactivity, nucleation of fine particulate matter 2.5 (PM 2.5 ), and implications for human health, but its chemical nature and relatively short lifetime make direct measurement of atmospheric ammonia difficult. During the 2015 NASA Student Airborne Research Program (SARP) an airborne miniature Chemical Ionization Mass Spectrometer (miniCIMS) was deployed on the NASA DC-8 flying laboratory in the Southern California region. The spatial and temporal variability of measured atmospheric ammonia concentrations will be discussed.

  4. Real-time monitoring of volatile organic compounds using chemical ionization mass spectroscopy: Final report

    Energy Technology Data Exchange (ETDEWEB)

    Thornberg, S.M.; Mowry, C.D.; Keenan, M.R.; Bender, S.F.A. [Sandia National Labs., Albuquerque, NM (United States). Gas Analysis Lab.; Owen, T. [Intel Corp., Rio Rancho, NM (United States)

    1997-04-01

    Volatile organic compound (VOC) emission to the atmosphere is of great concern to semiconductor manufacturing industries, research laboratories, the public, and regulatory agencies. Some industries are seeking ways to reduce emissions by reducing VOCs at the point of use (or generation). This paper discusses the requirements, design, calibration, and use of a sampling inlet/quadrupole mass spectrometer system for monitoring VOCs in a semiconductor manufacturing production line. The system uses chemical ionization to monitor compounds typically found in the lithography processes used to manufacture semiconductor devices (e.g., acetone, photoresist). The system was designed to be transportable from tool to tool in the production line and to give the operator real-time feedback so the process(es) can be adjusted to minimize VOC emissions. Detection limits ranging from the high ppb range for acetone to the low ppm range fore other lithography chemicals were achieved using chemical ionization mass spectroscopy at a data acquisition rate of approximately 1 mass spectral scan (30 to 200 daltons) per second. A demonstration of exhaust VOC monitoring was performed at a working semiconductor fabrication facility during actual wafer processing.

  5. GoAmazon 2014/15 Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) Field Campaign Report

    Energy Technology Data Exchange (ETDEWEB)

    Smith, JN [Univ. of California, Irvine, CA (United States)

    2016-04-01

    The Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) deployment to the U.S. Department of Energy (DOE)’s Atmospheric Radiation Measurement (ARM) Climate Research Facility T3 site in Manacapuru, Brazil, was motivated by two main scientific objectives of the Green Ocean Amazon (GoAmazon) 2014/15 field campaign. 1) Study the interactions between anthropogenic and biogenic emissions by determining important molecular species in ambient nanoparticles. To address this, TDCIMS data will be combined with coincident measurements such as gas-phase sulfuric acid to determine the contribution of sulfuric acid condensation to nucleation and growth. We can then compare that result to TDCIMS-derived nanoparticle composition to determine the fraction of growth that can be attributed to the uptake of organic compounds. The molecular composition of sampled particles will also be used to attribute specific chemical species and mechanisms to growth, such as the condensation of low-volatility species or the oligomerization of α-dicarbonyl compounds. 2) Determine the source of new ambient nanoparticles in the Amazon. The hypothesis prior to measurements was that potassium salts formed from the evaporation of primary particles emitted by fungal spores can provide a unique and important pathway for new particle production in the Amazon basin. To explore this hypothesis, the TDCIMS recorded the mass spectra of sampled ambient particles using a protonated water cluster Chemical Ionization Mass Spectrometer (CIMS). Laboratory tests performed using potassium salts show that the TDCIMS can detect potassium with high sensitivity with this technique.

  6. Determination of sulfonamides in meat by liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry

    International Nuclear Information System (INIS)

    Liquid chromatography/atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) has been used for the determination of sulfonamides in meat. Five typical sulfonamides were selected as target compounds, and beef meat was selected as a matrix sample. As internal standards, sulfapyridine and isotope labeled sulfamethazine (13C6-SMZ) were used. Compared to the results of recent reports, our results have shown improved precision to a RSD of 1.8% for the determination of sulfamethazine spiked with 75 ng/g level in meat

  7. Effects of ionizing radiation in the physico-chemical characteristics of red wine Cabernet Sauvignon

    International Nuclear Information System (INIS)

    The oenology in the current days is increasingly aimed obtain improvements on wine quality produced without there the deterioration of characteristics of the same, using new technologies for such order. The objective of present work will be the application of the radiation ionizing in wines Cabernet Sauvignon, with the interest of analyzing its effects on physic-chemical characteristics of this wines, such as quality, aging and etc. Were analyzed the following strands: degree alcoholic; dry extract; density and absorbance with spectrometer (420, 520 and 620 nm). (author)

  8. Simultaneous Measurement of Serum Chemical Castration Agents and Testosterone Levels Using Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry.

    Science.gov (United States)

    Ko, Dae-Hyun; Lee, Kyunghoon; Jeon, Sun-Hee; Song, Sang Hoon; Yun, Yeo-Min; Chun, Sail; Kim, Hee Seung; Kim, Jin Young; In, Moon Kyo; Song, Junghan

    2016-05-01

    Chemical castration involves administration of drugs to prevent pathological sexual behavior, reduce abnormal sexual drive and treat hormone-dependent cancers. Various drugs have been used for chemical castration; however, substantial interindividual variability and side effects are often observed. In this study, we proposed a useful monitoring method for the application of chemical castration agents using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS-MS). Testosterone, cyproterone acetate, medroxyprogesterone, goserelin acetate, leuprolide acetate and triptorelin acetate were analyzed by UPLC-MS-MS. The target drugs were extracted from serum samples by double protein precipitation using methanol. Testosterone-1,2-d2 and buserelin acetate were used as internal standards. Parameters of analytical performance were evaluated, including imprecision, linearity, ion suppression and detection capabilities. Testosterone measurements were compared with the results of immunoassays. Serum specimens from 51 subjects who underwent chemical castration were analyzed. All drugs and testosterone were well extracted and separated using our method. The method was essentially free from potential interferences and ion suppression. Within-run and between-run imprecision values were <15%. The lower limits of quantification were 0.125 and 0.5-1.0 ng/mL for testosterone and other drugs, respectively. Good correlations with pre-existing immunoassays for testosterone measurement were observed. Sera from subjects who underwent androgen deprivation therapy showed variable levels of drugs. We successfully developed a UPLC-MS-MS-based monitoring method for chemical castration. The performance of our method was generally acceptable. This method may provide a novel monitoring strategy for chemical castration to enhance expected effects while reducing unwanted side effects. PMID:26989223

  9. A Thermal Desorption Chemical Ionization Mass Spectrometer for the In Situ Measurement of Aerosol Organic Compounds

    Science.gov (United States)

    Thornberry, T.; Murphy, D. M.; Lovejoy, E. R.

    2005-12-01

    Organic material has been observed to comprise a significant fraction of organic aerosol mass in many regions of the troposphere. The organic compounds that comprise the organic fraction of atmospheric aerosol have the potential to affect the radiative and microphysical properties of the aerosol, with concomitant impacts on the role of the aerosol in climate forcing through direct and indirect effects. Knowledge of the organic compounds in atmospheric aerosols and their spatial distribution is needed to determine their effect on aerosol properties as well as to elucidate the role of aerosols in the chemistry of the atmosphere. The speciated measurement of aerosol organic compounds poses a significant experimental challenge due to the complexity and large number of organic species, and the low concentration at which individual species are present. A prototype instrument has been designed and built to make in situ speciated measurements of aerosol organic compounds. The instrument is composed of an aerosol collection/thermal desorption inlet coupled to a custom chemical ionization ion trap mass spectrometer. Aerosols are collected over a variable time by impaction on a target stage. The stage is then rapidly heated to volatilize the organic compounds into a small flow of helium carrier gas and conveyed to an ion-molecule reaction drift tube where proton transfer from H3O+ is used to softly ionize organic species. The ionized analyte molecules are then trapped and mass analyzed using a quadrupole ion trap. Results from preliminary experiments using laboratory-generated aerosol will be discussed

  10. Liquid chromatography-electrospray ionization-tandem mass spectrometry for simultaneous analysis of chlorogenic acids and their metabolites in human plasma.

    Science.gov (United States)

    Matsui, Yuji; Nakamura, Shun; Kondou, Naoki; Takasu, Yoshio; Ochiai, Ryuji; Masukawa, Yoshinori

    2007-10-15

    A method using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) was developed for the simultaneous analysis of nine chlorogenic acids (CGAs), three isomers each of caffeoylquinic acids (CQAs), feruloylquinic acids (FQAs) and dicaffeoylquinic acids (dCQAs), and their two metabolites, caffeic acid (CA) and ferulic acid (FA), in human plasma. In simultaneous multiple reaction monitoring (MRM) measurements using ESI-MS/MS with a negative ion mode, a deprotonated molecular ion derived from each of the 11 molecules was used as a precursor ion while three diagnostic product ions characteristic for each were selected for the qualitative analysis. To obtain maximal intensities for all diagnostic product ions, the collision energy was optimized for each one. LC separation was achieved under conditions of a reversed-phase Inertsil ODS-2 column combined with a gradient elution system using 50mM acetic acid with 3% acetonitrile aqueous solution and 50 mM acetic acid with 100% acetonitrile. In the quantitative analysis, one of the three diagnostic product ions for each of the 11 molecules was selected. Application of simultaneous LC-ESI-MS/MS MRM measurements to analyze the 11 standards spiked into blank human plasma indicated that all diagnostic product ions were detected without any interference, and that the sensitivity, linearity and recovery of this method were acceptable. When using this method to analyze those 11 molecules in the plasma after oral ingestion of 250 ml of a drink containing a green coffee bean extract (300 mg CGAs), all 11 molecules were identified and CQAs, FQAs and FA were quantified. CQAs, FQAs and dCQAs in human plasma were detected for the first time. This method should be useful to understand the biological and pharmacological effects of CGAs, such as improvement of human hypertension. PMID:17766198

  11. Precolumn derivatization reagents for high-speed analysis of amines and amino acids in biological fluid using liquid chromatography/electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Shimbo, Kazutaka; Oonuki, Takashi; Yahashi, Akihisa; Hirayama, Kazuo; Miyano, Hiroshi

    2009-05-01

    A rapid analytical method for amines and amino acids was developed, involving derivatization with the novel reagent 3-aminopyridyl-N-hydroxysuccinimidyl carbamate (APDS), followed by reversed-phase high-performance liquid chromatography and electrospray ionization tandem mass spectrometry (HPLC/ESI-MS/MS). More than 100 different analytes with amino groups, including amino acids in biological fluids such as mammalian plasma, could be measured within 10 min. The analytes were easily derivatized with APDS under the mild conditions. Selective reaction monitoring of ESI-MS/MS in positive mode was carried out to include the transitions of all of the protonated molecular ions of analytes derivatized with APDS to the common fragment at m/z 121, which was derived from the amino pyridyl moiety of the reagent. We evaluated the retention time precision, the quantification limits, the linearity, the intra- and inter-day precisions and the accuracy of 22 typical amino acids found in biological fluids, by analyzing a standard amino acid mixture and rat plasma. The intra-day relative standard deviations (RSDs) of the retention times of the 22 amino acids and their internal standards were within 0.9% and the inter-day RSDs were less than 1.1%, except for asparagines, with an RSD of 1.9%. The intra-day and inter-day RSDs of amino acid analyses in rat plasma were within 8.0% and 4.5%, respectively. The method, which facilitates the amino acid analysis of more than 100 samples in a day, represents an alternative to traditional amino acid analysis techniques, such as chromatography using postcolumn derivatization by ninhydrin. PMID:19350529

  12. N-alkylpyridinium quaternization combined with liquid chromatography–electrospray ionization-tandem mass spectrometry: A highly sensitive method to quantify fatty alcohols in thyroid tissues

    International Nuclear Information System (INIS)

    Highlights: • N-alkylpyridinium quaternization was combined with LC–ESI-MS/MS analysis to quantify fatty alcohols. • This method lowered the detection limits of fatty alcohols to 0.25 pg mL−1. • Ten kinds of even carbon-numbered fatty alcohols (C8–C24) were detected in human thyroid tissues. • Concentrations of fatty alcohols (free and esterified) in thyroid carcinoma tissues were lower than those in paired para-carcinoma tissues (p < 0.05). - Abstract: A highly sensitive method was developed for the identification and quantification of fatty alcohols in biological tissues. In the presence of pyridine-d0 and triflic anhydride (Tf2O), fatty alcohols were converted into permanently charged N-alkylpyridinium ions. Stable isotope-labeled derivatives were generated by pyridine-d5 and added as internal standard (IS). The mixture was analyzed by liquid chromatography coupled to positive electrospray ionization tandem mass spectrometry (LC–ESI-MS/MS). This method was optimized and validated in terms of reaction time, derivatization efficiency, stability, desalting, and ion suppression effect. Besides, fatty alcohols exhibited good linear relationship (r2 > 0.993) over the concentration range of 10 ng mL−1–1 μg mL−1. The limits of detection (LODs) were lowered from previously reported 0.1 ng mL−1 to 0.25 pg mL−1. Precision (RSD% < 15.6%), accuracy (93.0–107.2%), matrix effect, and recovery (in thyroid tissues) were validated as well. Finally, this method was applied for the analysis of ten even carbon-numbered fatty alcohols (C8–C24) in human thyroid carcinoma and para-carcinoma tissues, revealing a significant decrease of fatty alcohols (free and esterified) in thyroid carcinoma tissues (p < 0.05)

  13. Simultaneous Determination of Eight Ginsenosides in Rat Plasma by Liquid Chromatography–Electrospray Ionization Tandem Mass Spectrometry: Application to Their Pharmacokinetics

    Directory of Open Access Journals (Sweden)

    Li-Yuan Ma

    2015-12-01

    Full Text Available A high-performance liquid chromatography–electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS method was successfully developed and validated for the identification and determination of eight ginsenosides: ginsenoside Rg1 (1; 20(S-ginsenoside Rh1 (2; 20(S-ginsenoside Rg2 (3; 20(R-ginsenoside Rh1 (4; 20(R-ginsenoside Rg2 (5; ginsenoside Rd (6; 20(S-ginsenoside Rg3 (7; and 20(R-ginsenoside Rg3 (8 in rat plasma. The established rapid method had high linearity, selectivity, sensitivity, accuracy, and precision. The method has been used successfully to study the pharmacokinetics of abovementioned eight ginsenosides for the first time. After an oral administration of total saponins in the stems-leaves of Panax ginseng C. A. Meyer (GTSSL at a dose of 400 mg/kg, the ginsenosides 6, 7, and 8, belonging to protopanaxadiol-type saponins, exhibited relatively long tmax values, suggesting that they were slowly absorbed, while the ginsenosides 1–5, belonging to protopanaxatriol-type saponins, had different tmax values, which should be due to their differences in the substituted groups. Compounds 2 and 4, 3 and 5, 7 and 8 were three pairs of R/S epimerics at C-20, which was interesting that the t1/2 of 20(S-epimers were always longer than those of 20(R-epimers. This pharmacokinetic identification of multiple ginsenosides of GTSSL in rat plasma provides a significant basis for better understanding the clinical application of GTSSL.

  14. Identification and quantification of the major constituents in Egyptian carob extract by liquid chromatography–electrospray ionization-tandem mass spectrometry

    Directory of Open Access Journals (Sweden)

    Asmaa Ibrahim Owis

    2016-01-01

    Full Text Available Background: Carob - Ceratonia siliqua L., commonly known as St John's-bread or locust bean, family Fabaceae - is one of the most useful native Mediterranean trees. There is no data about the chromatography methods performed by high performance liquid chromatography (HPLC for determining polyphenols in Egyptian carob pods. Objective: To establish a sensitive and specific liquid chromatography–electrospray ionization (ESI-tandem mass spectrometry (MSn methodology for the identification of the major constituents in Egyptian carob extract. Materials and Methods: HPLC with diode array detector and ESI-mass spectrometry (MS was developed for the identification and quantification of phenolic acids, flavonoid glycosides, and aglycones in the methanolic extract of Egyptian C. siliqua. The MS and MSn data together with HPLC retention time of phenolic components allowed structural characterization of these compounds. Peak integration of ions in the MS scans had been used in the quantification technique. Results: A total of 36 compounds were tentatively identified. Twenty-six compounds were identified in the negative mode corresponding to 85.4% of plant dry weight, while ten compounds were identified in the positive mode representing 16.1% of plant dry weight, with the prevalence of flavonoids (75.4% of plant dry weight predominantly represented by two methylapigenin-O-pentoside isomers (20.9 and 13.7% of plant dry weight. Conclusion: The identification of various compounds present in carob pods opens a new door to an increased understanding of the different health benefits brought about by the consumption of carob and its products.

  15. Identification and quantification of glucosamine in rabbit cartilage and correlation with plasma levels by high performance liquid chromatography-electrospray ionization-tandem mass spectrometry

    International Nuclear Information System (INIS)

    Graphical abstract: Highlights: → Optimization of an HPLC-ESI-MS/MS method for glucosamine in rabbit cartilage. → Application of the method to an in-vivo study. → Glucosamine presence in cartilage in physiological condition. → Significant increase of cartilage glucosamine concentration after dosing. → Good correlation between cartilage glucosamine levels and plasma concentrations. - Abstract: A new HPLC-ESI-MS/MS method for the determination of glucosamine (2-amino-2-deoxy-D-glucose) in rabbit cartilage was developed and optimized. Glucosamine was extracted from cartilage by cryogenic grinding followed by protein precipitation with trichloroacetic acid. The HPLC separation was achieved with a polymer-based amino column using a mobile phase composed of 10 mM ammonium acetate (pH 7.5)-acetonitrile (20:80%, v/v) at 0.3 mL min-1 flow rate. D-[1-13C]Glucosamine was used as internal standard. Selective detection was performed by tandem mass spectrometry with electrospray source, operating in positive ionization mode and in multiple reaction monitoring acquisition (m/z 180 → 72 and 181 → 73 for glucosamine and internal standard, respectively). Limit of quantification was 0.045 ng injected, corresponding to 0.25 μg g-1 in cartilage. Linearity was obtained up to 20 μg g-1 (R2 > 0.991). Precision values (%R.S.D.) were -1 (n = 6). Glucosamine was present in cartilage in physiological condition before the treatment. After dosing, mean concentration of cartilage glucosamine significantly increased from 461 to 1040 ng g-1. Cartilage glucosamine levels resulted to be well correlated with plasma concentrations, which therefore are useful to predict the target cartilage concentration and its pharmacological activity.

  16. Multi-residue analysis of eight anticoagulant rodenticides in animal plasma and liver using liquid chromatography combined with heated electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Vandenbroucke, Virginie; Desmet, Noël; De Backer, Patrick; Croubels, Siska

    2008-06-15

    A sensitive method for the simultaneous quantification of eight anticoagulant rodenticides (brodifacoum, bromadiolone, chlorophacinone, coumatetralyl, difenacoum, difethialone, flocoumafen and warfarin) in animal plasma and liver using liquid chromatography combined with heated electrospray ionization tandem mass spectrometry (LC-HESI-MS/MS) is described. The sample preparation includes a liquid-liquid extraction with acetone. The compound 7-acetoxy-6-(2,3-dibromopropyl)-4,8-dimethylcoumarin is used as an internal standard. Chromatographic separation was achieved using a Nucleodur C18 gravity column. Good linearity was observed up to 750 ng mL(-1) for chlorophacinone and up to 500 ng mL(-1) for the other compounds in plasma. In liver, good linearity was seen up to 500 ng g(-1) for brodifacoum, chlorophacinone, difenacoum and difethialone and up to 750 ng g(-1) for the other compounds. Depending on the compound, a level of 1 or 5 ng mL(-1) could be quantified fulfilling the criteria for accuracy and precision and was therefore set as limit of quantification of the method in plasma. In liver, the limit of quantification was set at 250 ng g(-1) for coumatetralyl and warfarin and at 100 ng g(-1) for the other compounds. In plasma, the limit of detection varied from 0.07 ng mL(-1) for flocoumafen to 3.21 ng mL(-1) for brodifacoum. In liver, the limit of detection varied from 0.37 ng g(-1) for warfarin to 4.64 ng g(-1) for chlorophacinone. The method was shown to be of use in a pharmacokinetic study after single oral administration to mice and in the confirmation of suspected poisoning cases in domestic animals. PMID:18502701

  17. Effects of tetrafluorodibromoethane on the chemical ionization and chemiluminescence in propane-butane-air flames

    Energy Technology Data Exchange (ETDEWEB)

    Fialkov, A.B.; Fialkov, B.S.; Zinov' ev, L.A.

    1984-05-01

    In this paper, the effects of the inhibitor C/sub 2/F/sub 4/Br/sub 2/ on chemical ionization and chemical excitation occuring in propane-butane-air flames are considered. Flames burning at atmospheric pressure in a cylindrical burner were used as well as flames at 40-500 mm Hg with a planar matrix burner. The inhibitor vapor was supplied to the flow of fuel-air mixture from a heated cell. The inhibitor flow rate was determined by a gravimetric method. The emission intensities from CH* and C/sub 2/* and the concentration of positive ions as a function of tetrafluorodibromoethane flow rate indicate that the reaction for the formation of the primary CHO/sup +/ ion involves the HO/sub 2/ radical formed in the reaction H + O/sub 2/ + M ..-->.. HO/sub 2/ + M, whose rate is dependent on (H) and consequently on the inhibitor flow rate.

  18. From consumption to harvest: Environmental fate prediction of excreted ionizable trace organic chemicals

    DEFF Research Database (Denmark)

    Polesel, Fabio; Plósz, Benedek G.; Trapp, Stefan

    2015-01-01

    with freshwater or reclaimed wastewater. Recent research has shown the tendency for these substances to accumulate in food crops. In this study, we developed and applied a simulation tool to predict the fate of three ionizable trace chemicals (triclosan-TCS, furosemide-FUR, ciprofloxacin-CIP) from human...... the relative translocation of FUR to plant (45.3%-48.9% of emission to soil), as compared to sludge application (21.9%-27.6%). A comparison with peer-reviewed literature showed that model predictions were close to experimental data for elimination in WWTP, concentrations in sewage and sludge...... and bioconcentration factors (BCFs) in plant tissues, which showed however a large variability. The simulation tool presented here can thus be useful for priority setting and for the estimation of human exposure to trace chemicals via intake of food crops....

  19. Defence biochemical mechanisms of the organisms against chemical pollution and ionizing radiations

    International Nuclear Information System (INIS)

    Acute exposure to high concentrations / doses of chemical pollutants and ionizing radiation usually kills giving no chance for survival, if not immediately, than later followed by specific diseases. Fortunately, this acute exposure is accidental, but chronic, low level exposure is also damaging. The involvement of pollution, especially of chemically produced, one in the etiology of several diseases is still under intensive research. Compared to other kinds of pollution (radioactive, microbiological), the chemical one seldom kills suddenly; it acts slowly, silently, by accumulation into the tissues, eventually inducing a failure of certain organ. The body is continuously adapting to low level concentrations of chemicals from environment until a certain threshold. All organisms, including humans, have a limited capacity of resisting the effects of various types of pollutants. Extensive laboratory research, demonstrated that most of damaging organic pollutants cause the formation of free radicals when they penetrate into the body and are metabolized. Free radicals are very reactive and are known to damage tissues with potentially fatal results. Substantial experimental evidence in recent years has demonstrated that all organisms are endowed with versatile, efficient antioxidant systems, that provide protection against the formation or effects of free radicals. However, the antioxidant systems are limited and when their capacity of protection is exceeded, injury resulting in illness or death occurs. In most cases, the harmful effects of chemicals on organisms depend on the biotransformation step, where free radicals are produced as byproducts of the metabolic reactions. The damaging effects of chemical pollutants are mostly restricted to an important organ depending on the way of penetration, nature of the compound and concentration. The organisms possess specific and nonspecific defense systems, which act from the exposure step, with attempt to block the entry of

  20. A chemical ionization mass spectrometer for continuous underway shipboard analysis of dimethylsulfide in near-surface seawater

    OpenAIRE

    E. S. Saltzman; W. J. De Bruyn; Lawler, M J; Marandino, C. A.; McCormick, C. A.

    2009-01-01

    A compact, low-cost atmospheric pressure, chemical ionization mass spectrometer ("mini-CIMS") has been developed for continuous underway shipboard measurements of dimethylsulfide (DMS) in seawater. The instrument was used to analyze DMS in air equilibrated with flowing seawater across a porous Teflon membrane equilibrator. The equilibrated gas stream was diluted with air containing an isotopically-labeled internal standard. DMS is ionized at atmospheric pressure via proton transfer ...

  1. Relative mutagenic effects of ionizing radiations and alkylating chemicals in rice

    International Nuclear Information System (INIS)

    Studies were undertaken on the relative mutagenic effects of three ionizing radiations (X-rays, gamma rays, fast neutrons) and five alkylating chemicals (DES, EMS, MMS, NMH, MNNG) in rice. Observations on seed germination, seedling survival, seedling height, seed fertility and chlorophyll deficient chimeras were made in the M1 generation. The M2 generation was grown as M1 ear progenies. Chlorophyll mutation frequency, segregation percentage and mutant spectrum were estimated. The mutagenic effectiveness and efficiency were also worked out. Radiations were more effective than chemical mutagens. Mutagenic effectiveness decreased with increase in doses of mutagens. This was due to the failure of mutation frequency to increase proportionately with increase in mutagen doses. Mutagenic efficiency was higher for radiations when estimated on the basis of lethality and injury whereas, based on sterility, chemical mutagens were more efficient. Mutagenic efficiency also decreased with increase in doses of mutagens. The most effective as well as efficient radiation was fast neutrons. Among chemical mutagens the most effective was NMH whereas the most efficient was EMS. (author)

  2. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    Science.gov (United States)

    Rondo, L.; Ehrhart, S.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.

    2016-03-01

    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4-H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self-contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.

  3. Sensitivity effects in Uk'37 paleotemperature estimation by chemical ionization mass spectrometry.

    Science.gov (United States)

    Chaler, R; Grimalt, J O; Pelejero, C; Calvo, E

    2000-12-15

    Analysis of C37 alkenone mixtures by gas chromatography (GC) with flame ionization detection (FID) and GC coupled to mass spectrometry (GC/MS) in the chemical ionization mode (CI) shows that the later is useful for paleotemperature estimation when ammonia is used as reagent gas. Conversely, the use of isobutane gives rise to Uk'37 readings that are dependent on the amount of C37 alkenones introduced in the system, being unreliable for paleoclimatic studies. However, ammonia CI GC/MS may produce Uk'37 measurements that deviate from those obtained by GC-FID, the method calibrated for temperature estimation from algal cultures and marine sedimentary data. The differences result from changes in relative sensitivity between the di- and triunsaturated alkenones and depend on the instrument used and operational conditions. This problem is solved in the present study by determination of the response factor linear equations for each alkenone and their average relative sensitivity (R) using mixtures of known composition. These parameters allow the transformation of the GC/MS readings into the GC-FID equivalents using the following equation: UG = R x UM/(1 - UM(1 - R)). Examples of the suitability of this approach are given. PMID:11140754

  4. Universal imaging: Dissociative ionization of polyatomic molecules, chemical dynamics beamline 9.0.2

    International Nuclear Information System (INIS)

    A third endstation was recently added to the Chemical Dynamics beamline, designed to exploit the high flux broadband undulator light for a range of studies of reactive scattering, photochemistry and photoionization processes using time-of-flight mass spectroscopy coupled with position-sensitive detection. Two molecular beam sources are fixed at right angles, with the undulator light, or laser beams, intersecting the molecular beams at 45 degrees. To date, beamline experiments have included a study of dissociative photoionization of a variety of molecules including N2O and SF6. In this mode, a single molecular beam source is used, with the tunable undulator light inducing, in SF6 for example, the process SF6 → SF6+ + e- → SF5+ + F + e-. The SF5+ ions are accelerated up the flight tube, mass selected and detected as a function of position on a phosphor screen viewed by a CCD camera. The position directly reveals the recoil speed (or translational energy release) and angular distribution for the dissociative ionization process. Furthermore, this measurement is obtained for all recoil speeds and angles simultaneously. Such detailed angular information has not previously been obtained for dissociative ionization processes; typically ion time-of-flight profiles are deconvoluted to yield rough insight into the angular distributions. The recorded image is actually a 2-dimensional projection of the nascent 3-dimensional velocity distribution, but established tomographic techniques enable the authors to reconstruct the 3-D distribution

  5. Chemical abundances and properties of the ionized gas in NGC 1705

    CERN Document Server

    Annibali, F; Pasquali, A; Aloisi, A; Mignoli, M; Romano, D

    2015-01-01

    We obtained [O III] narrow-band imaging and multi-slit MXU spectroscopy of the blue compact dwarf (BCD) galaxy NGC 1705 with FORS2@VLT to derive chemical abundances of PNe and H II regions and, more in general, to characterize the properties of the ionized gas. The auroral [O III]\\lambda4363 line was detected in all but one of the eleven analyzed regions, allowing for a direct estimate of their electron temperature. The only object for which the [O III]\\lambda4363 line was not detected is a possible low-ionization PN, the only one detected in our data. For all the other regions, we derived the abundances of Nitrogen, Oxygen, Neon, Sulfur and Argon out to ~1 kpc from the galaxy center. We detect for the first time in NGC 1705 a negative radial gradient in the oxygen metallicity of -0.24 \\pm 0.08 dex kpc^{-1}. The element abundances are all consistent with values reported in the literature for other samples of dwarf irregular and blue compact dwarf galaxies. However, the average (central) oxygen abundance, 12 +...

  6. Determination of gardenia yellow colorants in soft drink, pastry, instant noodles with ultrasound-assisted extraction by high performance liquid chromatography-electrospray ionization tandem mass spectrum.

    Science.gov (United States)

    Zhou, Wei-E; Zhang, Yuan; Li, Yang; Ling, Yun; Li, Hong-Na; Li, Shao-Hui; Jiang, Shou-Jun; Ren, Zhi-Qin; Huang, Zhi-Qiang; Zhang, Feng

    2016-05-13

    A novel, rapid and simple analytical method was developed for the quantitative determination of crocin, crocetin and geniposide in soft drink, pastry and instant noodles. The solid samples were relatively homogenized into powders and fragments. The gardenia yellow colorants were successively extracted with methanol using ultrasound-assisted extraction. The analytes were quantitatively measured in the extracts by liquid chromatography coupled with electrospray ionization tandem mass spectrometry. High correlation coefficients (r(2)>0.995) of crocin, crocetin and geniposide were obtained within their linear ranges respectively (50-1000ng/mL, 50-1000ng/mL, 15-240ng/mL) by external standard method. The limits of detection (LODs) were 0.02μg/g for crocin, 0.01μg/g for crocetin and 0.002μg/g for geniposide. And the limits of quantitation (LOQs) were in the ranges of 0.05-0.45μg/g for crocin, and in the ranges of 0.042-0.32μg/g for crocetin, and in the ranges of 0.02-0.15μg/g for geniposide in soft drink, pastry and instant noodles samples. The average recoveries of crocin, crocetin and geniposide ranged from 81.3% to 117.6% in soft drink, pastry and instant noodles. The intra- and inter-day precisions were respectively in the range of 1.3-4.8% and 1.7-11.8% in soft drink, pastry and instant noodle. The developed methods were successfully validated and applied to the soft drink, pastry, and instant noodles collected from the located market in Beijing from China. Crocin, crocetin and geniposide were detected in the collected samples. The average concentrations ranged from 0.84 to 4.20mg/g for crocin, and from 0.62 to 3.11mg/g for crocetin, and from 0.18 to 0.79mg/g for gardenia in various food samples. The method can provide evidences for government to determine gardenia yellow pigments and geniposide in food. PMID:27086566

  7. Identification and quantification of glucosamine in rabbit cartilage and correlation with plasma levels by high performance liquid chromatography-electrospray ionization-tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Pastorini, Elisabetta; Vecchiotti, Stefania; Colliva, Carolina [Department of Pharmaceutical Sciences, University of Bologna, Via Belmeloro 6, I-40126 Bologna (Italy); Persiani, Stefano [Rottapharm-Madaus, Via Valosa di Sopra 9, 20900 Monza Brianza (Italy); Rotini, Roberto; Roatti, Giulia; Zaccarelli, Lorenzo [Division of Orthopedic Surgery (Section B), Rizzoli Orthopaedic Institute, Via Pupilli 1, 40136 Bologna (Italy); Rovati, Lucio Claudio [Rottapharm-Madaus, Via Valosa di Sopra 9, 20900 Monza Brianza (Italy); Roda, Aldo, E-mail: aldo.roda@unibo.it [Department of Pharmaceutical Sciences, University of Bologna, Via Belmeloro 6, I-40126 Bologna (Italy)

    2011-06-10

    Graphical abstract: Highlights: > Optimization of an HPLC-ESI-MS/MS method for glucosamine in rabbit cartilage. > Application of the method to an in-vivo study. > Glucosamine presence in cartilage in physiological condition. > Significant increase of cartilage glucosamine concentration after dosing. > Good correlation between cartilage glucosamine levels and plasma concentrations. - Abstract: A new HPLC-ESI-MS/MS method for the determination of glucosamine (2-amino-2-deoxy-D-glucose) in rabbit cartilage was developed and optimized. Glucosamine was extracted from cartilage by cryogenic grinding followed by protein precipitation with trichloroacetic acid. The HPLC separation was achieved with a polymer-based amino column using a mobile phase composed of 10 mM ammonium acetate (pH 7.5)-acetonitrile (20:80%, v/v) at 0.3 mL min{sup -1} flow rate. D-[1-{sup 13}C]Glucosamine was used as internal standard. Selective detection was performed by tandem mass spectrometry with electrospray source, operating in positive ionization mode and in multiple reaction monitoring acquisition (m/z 180 {yields} 72 and 181 {yields} 73 for glucosamine and internal standard, respectively). Limit of quantification was 0.045 ng injected, corresponding to 0.25 {mu}g g{sup -1} in cartilage. Linearity was obtained up to 20 {mu}g g{sup -1} (R{sup 2} > 0.991). Precision values (%R.S.D.) were <10%. Accuracy (% bias) ranged from -6.0% to 12%. Mean recoveries obtained at 3 concentration levels were higher than 81% (%R.S.D. {<=} 8%). The method was applied to measure glucosamine levels in rabbit cartilage and plasma after single oral administration of glucosamine sulfate at a dose of 98 mg kg{sup -1} (n = 6). Glucosamine was present in cartilage in physiological condition before the treatment. After dosing, mean concentration of cartilage glucosamine significantly increased from 461 to 1040 ng g{sup -1}. Cartilage glucosamine levels resulted to be well correlated with plasma concentrations, which

  8. Detection of trace levels of triclopyr using capillary gas chromatography-electron-capture negative-ion chemical ionization mass spectrometry.

    Science.gov (United States)

    Begley, P; Foulger, B E

    1988-04-01

    Triclopyr, after esterification, is shown to be a suitable candidate for detection by gas chromatography-electron-capture negative-ion chemical ionization mass spectrometry forming a characteristic carboxylate anion which offers a high detection sensitivity. A detection limit of 70 fg reaching the ionizer is indicated. Low backgrounds and an absence of chemical interferences are shown for vegetation extracts, using a simple method of extraction and derivatisation. A similar behaviour is demonstrated for 2,4-D and 2,4,5-T. PMID:3379116

  9. Demonstration of real-time monitoring of a photolithographic exposure process using chemical ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Mowry, C.D. [Sandia National Labs., Albuquerque, NM (United States). Analytical Chemistry Dept.

    1998-02-01

    Silicon wafers are coated with photoresist and exposed to ultraviolet (UV) light in a laboratory to simulate typical conditions expected in an actual semiconductor manufacturing process tool. Air is drawn through the exposure chamber and analyzed using chemical ionization mass spectrometry (CI/MS). Species that evaporate or outgas from the wafer are thus detected. The purpose of such analyses is to determine the potential of CI/MS as a real-time process monitoring tool. Results demonstrate that CI/MS can remotely detect the products evolved before, during, and after wafer UV exposure; and that the quantity and type of products vary with the photoresist coated on the wafer. Such monitoring could provide semiconductor manufacturers benefits in quality control and process analysis. Tool and photoresist manufacturers could also realize benefits from this measurement technique with respect to new tool, method, or photoresist development. The benefits realized can lead to improved device yields and reduced product and development costs.

  10. Tracing origins of complex pharmaceutical preparations using surface desorption atmospheric pressure chemical ionization mass spectrometry.

    Science.gov (United States)

    Zhang, Xinglei; Jia, Bin; Huang, Keke; Hu, Bin; Chen, Rong; Chen, Huanwen

    2010-10-01

    A novel strategy to trace the origins of commercial pharmaceutical products has been developed based on the direct chemical profiling of the pharmaceutical products by surface desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS). Besides the unambiguous identification of active drug components, various compounds present in the matrixes are simultaneously detected without sample pretreatment, providing valuable information for drug quality control and origin differentiation. Four sources of commercial amoxicillin products made by different manufacturers have been successfully differentiated. This strategy has been extended to secerning six sources of Liuwei Dihuang Teapills, which are herbal medicine preparations with extremely complex matrixes. The photolysis status of chemical drug products and the inferior natural herd medicine products prepared with different processes (e.g., extra heating) were also screened using the method reported here. The limit of detection achieved in the MS/MS experiments was estimated to be 1 ng/g for amoxicillin inside the capsule product. Our experimental data demonstrate that DAPCI-MS is a useful tool for rapid pharmaceutical analysis, showing promising perspectives for tracking the entire pharmaceutical supply chain to prevent counterfeit intrusions. PMID:20809628

  11. Pulse Operation of Chemical Oxygen-Iodine Laser by Pulsed Gas Discharge with the Assistance of Spark Pre-ionization

    Institute of Scientific and Technical Information of China (English)

    LI Guo-Fu; YU Hai-Jun; DUO Li-Ping; JIN Yu-Qi; WANG Jian; SANG Feng-Ting; FANG Ben-Jie; WANG De-Zhen

    2009-01-01

    The continuous wavelength chemical oxygen-iodine laser can be turned into pulse operation mode in order to obtain high energy and high pulse power. We propose an approach to produce iodine atoms instantaneously by pulsed gas discharge with the assistance of spark pre-ionization to achieve the pulsed goal. The influence of spark pre-ionization on discharge homogeneity is discussed. Voltage-current characteristics are shown and discussed in existence of the pre-ionization capacitor and peaking capacitor. The spark pre-ionization and peaking capacitor are very helpful in obtaining a stable and homogeneous discharge. The lasing is achieved at the total pressure of 2.2-2.9 kPa and single pulse energy is up to 180m J, the corresponding specific output energy is 1.0 J/L.

  12. [Development of a chemical ionization time-of-flight mass spectrometer for continuous measurements of atmospheric hydroxyl radical].

    Science.gov (United States)

    Dou, Jian; Hua, Lei; Hou, Ke-Yong; Jiang, Lei; Xie, Yuan-Yuan; Zhao, Wu-Duo; Chen, Ping; Wang, Wei-Guo; Di, Tian; Li, Hai-Yang

    2014-05-01

    A home-made chemical ionization time-of-flight mass spectrometer (TOFMS) has been developed for continuous measurements of atmospheric hydroxyl radical. Based on the atmospheric pressure chemical ionization technique, an ionization source with orthogonal dual tube structure was adopted in the instrument, which minimized the interference between the reagent gas ionization and the titration reaction. A 63Ni radioactive source was fixed inside one of the orthogonal tubes to generate reactant ion of NO(-)(3) from HNO3 vapor. Hydroxyl radical was first titrated by excess SO2 to form equivalent concentrations of H2SO4 in the other orthogonal tube, and then reacted with NO(-)(3) ions in the chemical ionization chamber, leading to HSO(-)(4) formation. The concentration of atmospheric hydroxyl radical can be directly calculated by measuring the intensities of the HSOj product ions and the NO(-)(3) reactant ions. The analytical capability of the instrument was demonstrated by measuring hydroxyl radical in laboratory air, and the concentration of the hydroxyl radical in the investigated air was calculated to be 1.6 x 106 molecules*cm ', based on 5 seconds integration. The results have shown that the instrument is competent for in situ continuous measurements of atmospheric trace radical. PMID:25055654

  13. Optimal choice of pH for toxicity and bioaccumulation studies of ionizing organic chemicals

    DEFF Research Database (Denmark)

    Rendal, Cecilie; Kusk, Kresten Ole; Trapp, Stefan

    2011-01-01

    processes were identified to explain the behavior of ionizing compounds with changing pH: the change in lipophilicity when a neutral compound becomes ionized, electrical attraction, and the ion trap. The literature was screened for bioaccumulation and toxicity tests of ionizing organic compounds performed...

  14. Effects of ionizing radiation on plastic food packaging materials: a review. 1. Chemical and physical changes

    International Nuclear Information System (INIS)

    Irradiation of prepackaged food causes chemical and physical changes in plastic packaging materials. The effects of ionizing radiation on these materials have been studied for almost 40 years; the respective literature is reviewed to provide the basis for a safety evaluation of plastics for use in food irradiation. Permeability of plastic films is generally not affected; deterioration of mechanical properties, that may occur with certain polymers, can usually be controlled with adequate stabilizers; and changes in infrared and UV/VIS spectra are slight at food irradiation doses. Gaseous radiolysis products include hydrogen, methane, CO2, CO, hydrocarbons, and for chlorine-containing polymers, hydrogen chloride. A range of volatile products, mainly hydrocarbons, alcohols, aldehydes, ketones, and carboxylic acids, has been characterized for low density polyethylene and polypropylene, other important materials, e.g., polystyrene and poly(vinyl chloride), are less well-investigated. Comparatively little is known on the effect of irradiation on multilayer structures. Radiation-induced changes are shown to depend on the chemical structure of the polymer, on the composition (additives) and processing history of the plastic, and on the irradiation conditions

  15. Chemical effects of ionizing radiation on the individual amino acids within intact and pure protein molecules. Final report

    International Nuclear Information System (INIS)

    Progress is reported on the following research projects: gamma radiation induced chemical and molecular weight changes in proteins; the free radical pattern for the irradiated protein; similarities in the mechanism of action of ionizing and of uv radiation; and spin trapping in the study of gamma radiolysis

  16. Localization of double bonds in triacylglycerols using high-performance liquid chromatography/atmospheric pressure chemical ionization ion-trap mass spectrometry.

    Science.gov (United States)

    Háková, Eva; Vrkoslav, Vladimír; Míková, Radka; Schwarzová-Pecková, Karolina; Bosáková, Zuzana; Cvačka, Josef

    2015-07-01

    A method for localizing double bonds in triacylglycerols using high-performance liquid chromatography-tandem mass spectrometry with atmospheric pressure chemical ionization (APCI) was developed. The technique was based on collision-induced dissociation or pulsed Q collision-induced dissociation of the C3H5N(+•) adducts ([M + 55](+•)) formed in the presence of acetonitrile in the APCI source. The spectra were investigated using a large series of standards obtained from commercial sources and prepared by randomization. The fragmentation spectra made it possible to determine (i) the total number of carbons and double bonds in the molecule, (ii) the number of carbons and double bonds in acyls, (iii) the acyl in the sn-2 position on the glycerol backbone, and (iv) the double-bond positions in acyls. The double-bond positions were determined based on two types of fragments (alpha and omega ions) formed by cleavages of C-C bonds vinylic to the original double bond. The composition of the acyls and their positions on glycerol were established from the masses and intensities of the ions formed by the elimination of fatty acids from the [M + 55](+•) precursor. The method was applied for the analysis of triacylglycerols in olive oil and vernix caseosa. PMID:25701424

  17. Universal imaging: Dissociative ionization of polyatomic molecules, chemical dynamics beamline 9.0.2

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, M.; Chen, D.; Suits, A.G. [Ernest Orlando Lawrence Berkeley National Lab., CA (United States)

    1997-04-01

    A third endstation was recently added to the Chemical Dynamics beamline, designed to exploit the high flux broadband undulator light for a range of studies of reactive scattering, photochemistry and photoionization processes using time-of-flight mass spectroscopy coupled with position-sensitive detection. Two molecular beam sources are fixed at right angles, with the undulator light, or laser beams, intersecting the molecular beams at 45{degrees}. To date, beamline experiments have included a study of dissociative photoionization of a variety of molecules including N{sub 2}O and SF{sub 6}. In this mode, a single molecular beam source is used, with the tunable undulator light inducing, in SF{sub 6} for example, the process SF{sub 6} {r_arrow} SF{sub 6}{sup +} + e{sup {minus}} {r_arrow} SF{sub 5}{sup +} + F + e{sup {minus}}. The SF{sub 5}{sup +} ions are accelerated up the flight tube, mass selected and detected as a function of position on a phosphor screen viewed by a CCD camera. The position directly reveals the recoil speed (or translational energy release) and angular distribution for the dissociative ionization process. Furthermore, this measurement is obtained for all recoil speeds and angles simultaneously. Such detailed angular information has not previously been obtained for dissociative ionization processes; typically ion time-of-flight profiles are deconvoluted to yield rough insight into the angular distributions. The recorded image is actually a 2-dimensional projection of the nascent 3-dimensional velocity distribution, but established tomographic techniques enable the authors to reconstruct the 3-D distribution.

  18. Capillary liquid chromatography-microchip atmospheric pressure chemical ionization-mass spectrometry.

    Science.gov (United States)

    Ostman, Pekka; Jäntti, Sirkku; Grigoras, Kestas; Saarela, Ville; Ketola, Raimo A; Franssila, Sami; Kotiaho, Tapio; Kostiainen, Risto

    2006-07-01

    A miniaturized nebulizer chip for capillary liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (capillary LC-microchip APCI-MS) is presented. The APCI chip consists of two wafers, a silicon wafer and a Pyrex glass wafer. The silicon wafer has a DRIE etched through-wafer nebulizer gas inlet, an edge capillary insertion channel, a stopper, a vaporizer channel and a nozzle. The platinum heater electrode and pads for electrical connection were patterned on to the Pyrex glass wafer. The two wafers were joined by anodic bonding, creating a microchip version of an APCI-source. The sample inlet capillary from an LC column is directly connected to the vaporizer channel of the APCI chip. The etched nozzle in the microchip forms a narrow sample plume, which is ionized by an external corona needle, and the formed ions are analyzed by a mass spectrometer. The nebulizer chip enables for the first time the use of low flow rate separation techniques with APCI-MS. The performance of capillary LC-microchip APCI-MS was tested with selected neurosteroids. The capillary LC-microchip APCI-MS provides quantitative repeatability and good linearity. The limits of detection (LOD) with a signal-to-noise ratio (S/N) of 3 in MS/MS mode for the selected neurosteroids were 20-1000 fmol (10-500 nmol l(-1)). LODs (S/N = 3) with commercial macro APCI with the same compounds using the same MS were about 10 times higher. Fast heat transfer allows the use of the optimized temperature for each compound during an LC run. The microchip APCI-source provides a convenient and easy method to combine capillary LC to any API-MS equipped with an APCI source. The advantages and potentials of the microchip APCI also make it a very attractive interface in microfluidic APCI-MS. PMID:16804601

  19. Airborne observations of formic acid using a chemical ionization mass spectrometer

    Directory of Open Access Journals (Sweden)

    M. Le Breton

    2012-12-01

    Full Text Available The first airborne measurements of formic acid mixing ratios over the United Kingdom were measured on the FAAM BAe-146 research aircraft on 16 March 2010 with a chemical ionization mass spectrometer using I reagent ions. The I ionization scheme was able to measure formic acid mixing ratios at 1 Hz in the boundary layer.

    In-flight standard addition calibrations from a formic acid source were used to determine the instrument sensitivity of 35 ± 6 ion counts pptv−1 s−1 and a limit of detection of 25 pptv. Routine measurements were made through a scrubbed inlet to determine the instrumental background. Three plumes of formic acid were observed over the UK, originating from London, Humberside and Tyneside. The London plume had the highest formic acid mixing ratio throughout the flight, peaking at 358 pptv. No significant correlations of formic acid with NOx and ozone were found, but a positive correlation was observed between CO and HCOOH within the two plumes where coincident data were recorded.

    A trajectory model was employed to determine the sources of the plumes and compare modelled mixing ratios with measured values. The model underestimated formic acid concentrations by up to a factor of 2. This is explained by missing sources in the model, which were considered to be both primary emissions of formic acid of mainly anthropogenic origin and a lack of precursor emissions, such as isoprene, from biogenic sources, whose oxidation in situ would lead to formic acid formation.

  20. Production and Utilization of CO3- Produced by a Corona Discharge in Air for Atmospheric Pressure Chemical Ionization

    Energy Technology Data Exchange (ETDEWEB)

    Ewing, Robert G.; Waltman, Melanie J.

    2010-12-14

    Atmospheric pressure chemical ionization is a multistep ionization process used in mass spectrometry and ion mobility spectrometry. The formation of product ions depends upon interactions with the analyte and the reactant ion species formed in the ionization source. The predominant reactant ion observed in a point-to-plane corona discharge in air occurs at m/z 60. There have been multiple references in the literature to the identity of this ion with some disagreement. It was postulated to be either CO3- or N2O2-. The identity of this ion is important as it is a key to the ionization of analytes. It was determined here to be CO3- through the use of 18O labeled oxygen. Further confirmation was provided through MS/MS studies. The ionization of nitroglycerine (NG) with CO3- produced the adduct NG•CO3-. This was compared to ionization with NO3- and Cl- reactant ions that also formed adducts with NG. The fragmentation patterns of these three adducts provides insight into the charge distribution and indicates that CO3- has a relatively high electron affinity similar to that of nitrate.

  1. Tandem virtual screening targeting the SRA domain of UHRF1 identifies a novel chemical tool modulating DNA methylation.

    Science.gov (United States)

    Myrianthopoulos, Vassilios; Cartron, Pierre Francois; Liutkevičiūtė, Zita; Klimašauskas, Saulius; Matulis, Daumantas; Bronner, Christian; Martinet, Nadine; Mikros, Emmanuel

    2016-05-23

    Ubiquitin-like protein UHRF1 that contains PHD and RING finger domain 1 is a key epigenetic protein enabling maintenance of the DNA methylation status through replication. A tandem virtual screening approach was implemented for identifying small molecules able to bind the 5-methylcytosine pocket of UHRF1 and inhibit its functionality. The NCI/DTP small molecules Repository was screened in silico by a combined protocol implementing structure-based and ligand-based methodologies. Consensus ranking was utilized to select a set of 27 top-ranked compounds that were subsequently evaluated experimentally in a stepwise manner for their ability to demethylate DNA in cellulo using PCR-MS and HPLC-MS/MS. The most active molecules were further assessed in a cell-based setting by the Proximity Ligation In Situ Assay and the ApoTome technology. Both evaluations confirmed that the DNMT1/UHRF1 interactions were significantly reduced after 4 h of incubation of U251 glioma cells with the most potent compound NSC232003, showing a 50% interaction inhibition at 15 μM as well as induction of global DNA cytosine demethylation as measured by ELISA. This is the first report of a chemical tool that targets UHRF1 and modulates DNA methylation in a cell context by potentially disrupting DNMT1/UHRF1 interactions. Compound NSC232003, a uracil derivative freely available by the NCI/DTP Repository, provides a versatile lead for developing highly potent and cell-permeable UHRF1 inhibitors that will enable dissection of DNA methylation inheritance. PMID:27049577

  2. Use of electron ionization and atmospheric pressure chemical ionization in gas chromatography coupled to time-of-flight mass spetrometry for screening and identification of organic pollutants in waters

    NARCIS (Netherlands)

    Portoles, T.; Mol, J.G.J.; Sancho, J.V.; Hernandez, F.

    2014-01-01

    A new approach has been developed for multiclass screening of organic contaminants in water based on the use of gas chromatography coupled to hybrid quadrupole high-resolution time-of-flight mass spectrometry with atmospheric pressure chemical ionization (GC–(APCI)QTOF MS). The soft ionization promo

  3. Influence of soil pH on the sorption of ionizable chemicals

    DEFF Research Database (Denmark)

    Franco, Antonio; Fu, Wenjing; Trapp, Stefan

    2009-01-01

    The soil-water distribution coefficient of ionizable chemicals (K-d) depends on the soil acidity, mainly because the pH governs speciation. Using pH-specific K-d values normalized to organic carbon (K-OC) from the literature, a method was developed to estimate the K-OC of monovalent organic acids...... and bases. The regression considers pH-dependent speciation and species-specific partition coefficients, calculated from the dissociation constant (pK(a)) and the octanol-water partition coefficient of the neutral molecule (log P-n). Probably because of the lower pH near the organic colloid......-water interface, the optimal pH to model dissociation was lower than the bulk soil pH. The knowledge of the soil pH allows calculation of the fractions of neutral and ionic molecules in the system, thus improving the existing regression for acids. The same approach was not successful with bases, for which the...

  4. Mechanisms of chemical modification of neoplastic cell transformation by ionizing radiation

    International Nuclear Information System (INIS)

    During space travel, astronauts will be continuously exposed to ionizing radiation; therefore, it is necessary to minimize the radiation damage by all possible means. The authors' studies show that DMSO (when present during irradiation) can protect cells from being killed and transformed by X rays and that low concentration of DMSO can reduce the transformation frequency significantly when it is applied to cells, even many days after irradiation. The process of neoplastic cell transformation is a complicated one and includes at least two different stages: induction and expression. DMSO apparently can modify the radiation damage during both stages. There are several possible mechanisms for the DMSO effect: (1) changing the cell membrane structure and properties; (2) inducing cell differentiation by acting on DNA; and (3) scavanging free radicals in the cell. Recent studies with various chemical agents, e.g., 5-azacytidine, dexamethane, rhodamin-123, etc., indicate that the induction of cell differentiation by acting on DNA may be an important mechanism for the suppression of expression of neoplastic cell transformation by DMSO

  5. Atmospheric pressure chemical ionization of explosives using alternating current corona discharge ion source.

    Science.gov (United States)

    Usmanov, D T; Chen, L C; Yu, Z; Yamabe, S; Sakaki, S; Hiraoka, K

    2015-04-01

    The high-sensitive detection of explosives is of great importance for social security and safety. In this work, the ion source for atmospheric pressure chemical ionization/mass spectrometry using alternating current corona discharge was newly designed for the analysis of explosives. An electromolded fine capillary with 115 µm inner diameter and 12 mm long was used for the inlet of the mass spectrometer. The flow rate of air through this capillary was 41 ml/min. Stable corona discharge could be maintained with the position of the discharge needle tip as close as 1 mm to the inlet capillary without causing the arc discharge. Explosives dissolved in 0.5 µl methanol were injected to the ion source. The limits of detection for five explosives with 50 pg or lower were achieved. In the ion/molecule reactions of trinitrotoluene (TNT), the discharge products of NOx (-) (x = 2,3), O3 and HNO3 originating from plasma-excited air were suggested to contribute to the formation of [TNT - H](-) (m/z 226), [TNT - NO](-) (m/z 197) and [TNT - NO + HNO3 ](-) (m/z 260), respectively. Formation processes of these ions were traced by density functional theory calculations. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26149109

  6. Multiresidue analysis of pesticides in traditional Chinese medicines using gas chromatography - negative chemical ionization tandem mass spectrometry

    Science.gov (United States)

    In this study, a residue analysis method for the simultaneous determination of 107 pesticides in the traditional Chinese medicines (TCMs), Angelica sinensis, Angelica dahurica, Leonurus heterophyllus Sweet, Pogostemon cablin, and Lonicera japonica Thunb, was developed using gas chromatography couple...

  7. A corona discharge atmospheric pressure chemical ionization source with selective NO(+) formation and its application for monoaromatic VOC detection.

    Science.gov (United States)

    Sabo, Martin; Matejčík, Štefan

    2013-11-21

    We have developed a new type of corona discharge (CD) for atmospheric pressure chemical ionization (APCI) for application in ion mobility spectrometry (IMS) as well as in mass spectrometry (MS). While the other CD-APCI sources are able to generate H3O(+)·(H2O)n as the major reactant ions in N2 or in zero air, the present CD-APCI source has the ability to generate up to 84% NO(+)·(H2O)n reactant ions in zero air. The change of the working gas from zero air to N2 allows us to change the major reactant ions from NO(+)·(H2O)n to H3O(+)·(H2O)n. In this paper we present the description of the new CD-APCI and discuss the processes associated with the NO(+) formation. The selective formation of NO(+)·(H2O)n reactant ions offers chemical ionization based on these ions which can be of great advantage for some classes of chemicals. We demonstrate here a significant increase in the sensitivity of the IMS-MS instrument for monoaromatic volatile organic compound (VOC) detection upon NO(+)·(H2O)n chemical ionization. PMID:24081306

  8. Ionization mechanism of the ambient pressure pyroelectric ion source (APPIS) and its applications to chemical nerve agent detection.

    Science.gov (United States)

    Neidholdt, Evan L; Beauchamp, J L

    2009-11-01

    We present studies of the ionization mechanism operative in the ambient pressure pyroelectric ionization source (APPIS), along with applications that include detection of simulants for chemical nerve agents. It is found that ionization by APPIS occurs in the gas-phase. As the crystal is thermally cycled over a narrow temperature range, electrical discharges near the surface of the crystal produce energetic species which, through reactions with atmospheric molecules, result in reactant ions such as protonated water clusters or clusters of hydroxide and water. Reactant ions can be observed directly in the mass spectrometer. These go on to react with trace neutrals via proton transfer reactions to produce the ions observed in mass spectra, which are usually singly protonated or deprotonated species. Further implicating gas-phase ionization, observed product distributions are highly dependent on the composition of ambient gases, especially the concentration of water vapor and oxygen surrounding the source. For example, basic species such as triethylamine are observed as singly protonated cations at a water partial pressure of 10 torr. At a water pressure of 4 torr, reactive oxygen species are formed and lead to observation of protonated amine oxides. The ability of the APPIS source to detect basic molecules with high proton affinities makes it highly suited for the detection of chemical nerve agents. We demonstrate this application using simulants corresponding to VX and GA (Tabun). With the present source configuration pyridine is detected readily at a concentration of 4 ppm, indicating ultimate sensitivity in the high ppb range. PMID:19682922

  9. Chemical ionization mass spectrometry (CIMS) may not measure all gas-phase sulfuric acid if base molecules are present

    OpenAIRE

    Kurtén, T.; T. Petäjä; Smith,J; Ortega, I.K.; Sipilä, M.; Junninen, H.; M. Ehn; Vehkamäki, H.; Mauldin, L.; Worsnop, D.R.; M. Kulmala

    2010-01-01

    The state-of-the art method for measuring atmospheric gas-phase sulfuric acid is chemical ionization mass spectrometry (CIMS) based on nitrate reagent ions. Using computed proton affinities and reaction thermodynamics for the relevant charging reactions, we show that in the presence of strong bases such as amines, which tend to cluster with the sulfuric acid molecules, a significant fraction of the total gas-phase sulfuric acid may not be measured by a CIMS instrument. If this is the c...

  10. Investigation of the Reactivity of Oligodeoxynucleotides with Glyoxal and KMnO4 Chemical Probes by Electrospray Ionization Mass Spectrometry

    OpenAIRE

    Parr, Carol; Pierce, Sarah E.; Smith, Suncerae I.; Brodbelt, Jennifer S.

    2011-01-01

    The reactions of two well-known chemical probes, glyoxal and potassium permanganate (KMnO4), with oligodeoxynucleotides were monitored by electrospray ionization (ESI) mass spectrometry to evaluate the influence of the sequence of DNA, its secondary structure, and interactions with associated ligands on the reactivity of the two probes. Glyoxal, a guanine-reactive probe, incorporated a mass shift of 58 Da, and potassium permanganate (KMnO4) is a thymine-reactive probe that resulted in a mass ...

  11. A field-deployable, chemical ionization time-of-flight mass spectrometer

    Directory of Open Access Journals (Sweden)

    T. H. Bertram

    2011-07-01

    Full Text Available We constructed a new chemical ionization time-of-flight mass spectrometer (CI-TOFMS that measures atmospheric trace gases in real time with high sensitivity. We apply the technique to the measurement of formic acid via negative-ion proton transfer, using acetate as the reagent ion. A novel high pressure interface, incorporating two RF-only quadrupoles is used to efficiently focus ions through four stages of differential pumping before analysis with a compact TOFMS. The high ion-duty cycle (>20 % of the TOFMS combined with the efficient production and transmission of ions in the high pressure interface results in a highly sensitive (>300 ions s−1 pptv−1 formic acid instrument capable of measuring and saving complete mass spectra at rates faster than 10 Hz. We demonstrate the efficient transfer and detection of both bare ions and ion-molecule clusters, and characterize the instrument during field measurements aboard the R/V Atlantis as part of the CalNex campaign during the spring of 2010. The in-field short-term precision is better than 5 % at 1 pptv (pL/L, for 1-s averages. The detection limit (3 σ, 1-s averages of the current version of the CI-TOFMS, as applied to the in situ detection of formic acid, is limited by the magnitude and variability in the background determination and was determined to be 4 pptv. Application of the CI-TOFMS to the detection of other inorganic and organic acids, as well as the use of different reagent ion molecules (e.g. I, CF3O, CO3 is promising, as we have demonstrated efficient transmission and detection of both bare ions and their associated ion-molecule clusters.

  12. Atmospheric amines and ammonia measured with a Chemical Ionization Mass Spectrometer (CIMS

    Directory of Open Access Journals (Sweden)

    Y. You

    2014-06-01

    Full Text Available We report ambient measurements of amines and ammonia with a~fast response chemical ionization mass spectrometer (CIMS in a southeastern US forest in Alabama and a~moderately polluted Midwestern site during the summer. In the Alabama forest, mostly C3-amines (from pptv to tens of pptv and ammonia (up to 2 ppbv were detected on a daily basis. C3-amines and ammonia showed similar diurnal trends and temperature and wind direction dependences, and were not associated with transported CO and SO2 plumes. Consistent with temperature dependences, amine and ammonia in the gas and aerosol phases showed opposite diurnal trends, indicating gas-to-particle partitioning of amines and ammonia. Temperature dependences also imply reversible processes of amines and ammonia evaporation from soil surfaces in daytime and deposition of amines and ammonia to soil surfaces at nighttime. Various amines (C1–C6 at the pptv level were observed in the transported biomass burning plumes, showing that biomass burning can be a substantial source of amines in the Southeast US. At the moderately polluted Kent site, higher concentrations of amines (C1–C6, from pptv to tens of pptv and ammonia (up to 6 ppbv were detected. Diurnal variations of C1- to C3-amines and ammonia were correlated with the ambient temperature. C4- to C6-amines showed abrupt increases during the nighttime, suggesting that they were emitted from local sources. These abundant amines and ammonia may in part explain the frequent new particle formation events reported from Kent. Lower amine concentrations at the rural forested site highlight the importance of constraining anthropogenic sources of amines.

  13. Atmospheric Amines and Ammonia Measured with a Chemical Ionization Mass Spectrometer (CIMS)

    Energy Technology Data Exchange (ETDEWEB)

    You, Y.; Kanawade, V. P.; de Gouw, J. A.; Guenther, Alex B.; Madronich, Sasha; Sierra-Hernandez, M. R.; Lawler, M.; Smith, James N.; Takahama, S.; Ruggeri, G.; Koss, A.; Olson, K.; Baumann, K.; Weber, R. J.; Nenes, A.; Guo, H.; Edgerton, Eric S.; Porcelli, L.; Brune, W. H.; Goldstein, Allen H.; Lee, S.-H

    2014-11-19

    We report ambient measurements of amines and ammonia with a fast response chemical ionization mass spectrometer (CIMS) in a Southeastern U.S. forest in Alabama and a moderately polluted Midwestern site during the summer. In the Alabama forest, mostly C3-amines (from pptv to tens of pptv) and ammonia (up to 2 ppbv) were detected on a daily basis. C3-amines and ammonia showed similar diurnal trends and temperature and wind direction dependences, and were not associated with transported CO and SO2 plumes. Consistent with temperature dependences, amine and ammonia in the gas and aerosol phases showed opposite diurnal trends, indicating gas-to-particle partitioning of amines and ammonia. Temperature dependences also imply reversible processes of amines and ammonia evaporation from soil surfaces in daytime and deposition of amines and ammonia to soil surfaces at nighttime. Various amines (C1-C6) at the pptv level were observed in the transported biomass burning plumes, showing that biomass burning can be a substantial source of amines in the Southeast U.S. At the moderately polluted Kent site, higher concentrations of amines (C1-C6, from pptv to tens of pptv) and ammonia (up to 6 ppbv) were detected. Diurnal variations of C1- to C3-amines and ammonia were correlated with the ambient temperature. C4- to C6-amines showed abrupt increases during the nighttime, suggesting that they were emitted from local sources. These abundant amines and ammonia may in part explain the frequent new particle formation events reported from Kent. Lower amine concentrations at the rural forested site highlight the importance of constraining anthropogenic sources of amines.

  14. On-line characterization of gaseous and particulate organic analytes using atmospheric pressure chemical ionization mass spectrometry

    International Nuclear Information System (INIS)

    A modified atmospheric pressure chemical ionization ion source is applied for direct analysis of volatile or low volatile organic compounds in air. The method is based on the direct introduction of the analytes in the gas phase and/or particle phase into the ion source of a commercial ion-trap mass spectrometer. Two methods are employed for the production of primary ions at atmospheric pressure, photoionization and corona discharge. It is shown that in the presence of a dopant, photoionization can be a highly efficient ionization method also for real-time analysis with detection limits for selected analytes in the lower ppt-range. Using corona discharge for the production of primary ions, which is instrumentally easier since no additional chemicals have to be added to the sample flow, we demonstrate the analytical potential of on-line atmospheric pressure chemical ionization mass spectrometry for reaction monitoring experiments. To do so, an atmospherically relevant gas phase reaction is carried out in a 500 l reaction chamber and gaseous and particulate compounds are monitored in the positive and negative ion mode of the mass spectrometer

  15. In-Line Ozonation for Sensitive Air-Monitoring of a Mustard-Gas Simulant by Atmospheric Pressure Chemical Ionization Mass Spectrometry

    Science.gov (United States)

    Okumura, Akihiko

    2015-09-01

    A highly sensitive method for real-time air-monitoring of mustard gas (bis(2-chloroethyl) sulfide, HD), which is a lethal blister agent, is proposed. Humidified air containing a HD simulant, 2-chloroethyl ethyl sulfide (2CEES), was mixed with ozone and then analyzed by using an atmospheric pressure chemical ionization ion trap tandem mass spectrometer. Mass-spectral ion peaks attributable to protonated molecules of intact, monooxygenated, and dioxygenated 2CEES (MH+, MOH+, and MO2H+, respectively) were observed. As ozone concentration was increased from zero to 30 ppm, the signal intensity of MH+ sharply decreased, that of MOH+ increased once and then decreased, and that of MO2H+ sharply increased until reaching a plateau. The signal intensity of MO2H+ at the plateau was 40 times higher than that of MH+ and 100 times higher than that of MOH+ in the case without in-line ozonation. Twenty-ppm ozone gas was adequate to give a linear calibration curve for 2CEES obtained by detecting the MO2H+ signal in the concentration range up to 60 μg/m3, which is high enough for hygiene management. In the low concentration range lower than 3 μg/m3, which is equal to the short-term exposure limit for HD, calibration plots unexpectedly fell off the linear calibration curve, but 0.6-μg/m3 vapor was actually detected with the signal-to-noise ratio of nine. Ozone was generated from instrumentation air by using a simple and inexpensive home-made generator. 2CEES was ozonated in 1-m extended sampling tube in only 1 s.

  16. Selective and rapid determination of raltegravir in human plasma by liquid chromatography–tandem mass spectrometry in the negative ionization mode

    OpenAIRE

    Ajay Gupta; Swati Guttikar; Priyanka A. Shah; Gajendra Solanki; Pranav S. Shrivastav; Mallika Sanyal

    2015-01-01

    A selective and rapid high-performance liquid chromatography–tandem mass spectrometry method was developed and validated for the quantification of raltegravir using raltegravir-d3 as an internal standard (IS). The analyte and IS were extracted with methylene chloride and n-hexane solvent mixture from 100 µL human plasma. The chromatographic separation was achieved on a Chromolith RP-18e endcapped C18 (100 mm×4.6 mm) column in a run time of 2.0 min. Quantitation was performed in the negative i...

  17. Coupling an electrospray source and a solids probe/chemical ionization source to a selected ion flow tube apparatus

    International Nuclear Information System (INIS)

    A new ion source region has been constructed and attached to a variable temperature selected ion flow tube. The source features the capabilities of electron impact, chemical ionization, a solids probe, and electrospray ionization. The performance of the instrument is demonstrated through a series of reactions from ions created in each of the new source regions. The chemical ionization source is able to create H3O+, but not as efficiently as similar sources with larger apertures. The ability of this source to support a solids probe, however, greatly expands our capabilities. A variety of rhenium cations and dications are created from the solids probe in sufficient abundance to study in the flow tube. The reaction of Re+ with O2 proceeds with a rate constant that agrees with the literature measurements, while the reaction of Re22+ is found to charge transfer with O2 at about 60% of the collision rate; we have also performed calculations that support the charge transfer pathway. The electrospray source is used to create Ba+, which is reacted with N2O to create BaO+, and we find a rate constant that agrees with the literature

  18. Coupling an electrospray source and a solids probe/chemical ionization source to a selected ion flow tube apparatus

    Energy Technology Data Exchange (ETDEWEB)

    Melko, Joshua J.; Ard, Shaun G.; Shuman, Nicholas S.; Viggiano, Albert A., E-mail: afrl.rvborgmailbox@kirtland.af.mil [Air Force Research Laboratory, Space Vehicles Directorate, Kirtland AFB, New Mexico 87117-5776 (United States); Pedder, Randall E.; Taormina, Christopher R. [Ardara Technologies L.P., 12941 Route 993, Ardara, Pennsylvania 15615 (United States)

    2015-08-15

    A new ion source region has been constructed and attached to a variable temperature selected ion flow tube. The source features the capabilities of electron impact, chemical ionization, a solids probe, and electrospray ionization. The performance of the instrument is demonstrated through a series of reactions from ions created in each of the new source regions. The chemical ionization source is able to create H{sub 3}O{sup +}, but not as efficiently as similar sources with larger apertures. The ability of this source to support a solids probe, however, greatly expands our capabilities. A variety of rhenium cations and dications are created from the solids probe in sufficient abundance to study in the flow tube. The reaction of Re{sup +} with O{sub 2} proceeds with a rate constant that agrees with the literature measurements, while the reaction of Re{sub 2}{sup 2+} is found to charge transfer with O{sub 2} at about 60% of the collision rate; we have also performed calculations that support the charge transfer pathway. The electrospray source is used to create Ba{sup +}, which is reacted with N{sub 2}O to create BaO{sup +}, and we find a rate constant that agrees with the literature.

  19. Coupling an electrospray source and a solids probe/chemical ionization source to a selected ion flow tube apparatus

    Science.gov (United States)

    Melko, Joshua J.; Ard, Shaun G.; Shuman, Nicholas S.; Pedder, Randall E.; Taormina, Christopher R.; Viggiano, Albert A.

    2015-08-01

    A new ion source region has been constructed and attached to a variable temperature selected ion flow tube. The source features the capabilities of electron impact, chemical ionization, a solids probe, and electrospray ionization. The performance of the instrument is demonstrated through a series of reactions from ions created in each of the new source regions. The chemical ionization source is able to create H3O+, but not as efficiently as similar sources with larger apertures. The ability of this source to support a solids probe, however, greatly expands our capabilities. A variety of rhenium cations and dications are created from the solids probe in sufficient abundance to study in the flow tube. The reaction of Re+ with O2 proceeds with a rate constant that agrees with the literature measurements, while the reaction of Re22+ is found to charge transfer with O2 at about 60% of the collision rate; we have also performed calculations that support the charge transfer pathway. The electrospray source is used to create Ba+, which is reacted with N2O to create BaO+, and we find a rate constant that agrees with the literature.

  20. A chemical ionization mass spectrometer for continuous underway shipboard analysis of dimethylsulfide in near-surface seawater

    Directory of Open Access Journals (Sweden)

    E. S. Saltzman

    2009-11-01

    Full Text Available A compact, low-cost atmospheric pressure, chemical ionization mass spectrometer ("mini-CIMS" has been developed for continuous underway shipboard measurements of dimethylsulfide (DMS in seawater. The instrument was used to analyze DMS in air equilibrated with flowing seawater across a porous Teflon membrane equilibrator. The equilibrated gas stream was diluted with air containing an isotopically-labeled internal standard. DMS is ionized at atmospheric pressure via proton transfer from water vapor, then declustered, mass filtered via quadrupole mass spectrometry, and detected with an electron multiplier. The instrument described here is based on a low-cost residual gas analyzer (Stanford Research Systems, which has been modified for use as a chemical ionization mass spectrometer. The mini-CIMS has a gas phase detection limit of 220 ppt DMS for a 1 min averaging time, which is roughly equivalent to a seawater DMS concentration of 0.1 nM DMS at 20°C. The mini-CIMS has the sensitivity, selectivity, and time response required for underway measurements of surface ocean DMS over the full range of oceanographic conditions. The simple, robust design and relatively low cost of the instrument are intended to facilitate use in process studies and surveys, with potential for long-term deployment on research vessels, ships of opportunity, and large buoys.

  1. A chemical ionization mass spectrometer for continuous underway shipboard analysis of dimethylsulfide in near-surface seawater

    Directory of Open Access Journals (Sweden)

    E. S. Saltzman

    2009-07-01

    Full Text Available A compact, low-cost atmospheric pressure, chemical ionization mass spectrometer ("mini-CIMS" has been developed for continuous underway shipboard measurements of dimethylsulfide (DMS in seawater. The instrument was used to analyze DMS in air equilibrated with flowing seawater across a porous Teflon membrane equilibrator. The equilibrated gas stream was diluted with air containing an isotopically-labeled internal standard. DMS is ionized at atmospheric pressure via proton transfer from water vapor, then declustered, mass filtered via quadrupole mass spectrometry, and detected with an electron multiplier. The instrument described here is based on a low-cost residual gas analyzer (Stanford Research Systems, which has been modified for use as a chemical ionization mass spectrometer. The mini-CIMS has a gas phase detection limit of 170 ppt DMS for a 1 min averaging time, which is roughly equivalent to a seawater DMS concentration of 0.1 nM DMS at 20°C. The mini-CIMS has the sensitivity, selectivity, and time response required for underway measurements of surface ocean DMS over the full range of oceanographic conditions. The simple, robust design and relatively low cost of the instrument are intended to facilitate use in process studies and surveys, with potential for long-term deployment on research vessels, ships of opportunity, and large buoys.

  2. Some chemical influence on genetic effects of ionizing radiation and biodosimetry problems

    International Nuclear Information System (INIS)

    Complete text of publication follows. Radiation sensitivity is a quantitative character from genetic point of view and the distribution of this character values in populations is characterized by a binomial curve. So, 50% of the population have the mean values of radiosensitivity (x ± 0.67σ), 95% of individuals have radiosensitivity values equal to x ± 1.96σ and 5% of the population have this characters ranged from x ± 1.96σ to x ± 3σ, with division into the supersensitive fraction (2.5%) and the superresistant one (2.5%). Radiosensitivity as well as other quantitative characters is caused by the interaction of some pairs of polymeric genes determining a lot of physiological and biochemical organism features. Thus, irradiation in the same dose can induce different level of mutations or other biological effects in different humans. Besides, radiosensitivity depends to a great degree upon environmental factors. For instance, a level of radiosensitivity depends on physical activity, nervous and psychological state, hormonal balance etc. A diet can change an individual radioresistance - food rich in vitamins, microelements, adaptogens and so on favors the increase in individual radioresistance. Many food stuffs contain radioprotectors or antimutagens. So, tea, coffee, cocoa, chocolate, mushrooms and other products have melanin, which is a very effective radioprotector not only against acute irradiation, but even against chronic one according to out data. On the contrary some substances in our food such as residual amounts of fertilizers or herbicides can be mutagenic or increase mutagenic action of radiation. In the last case we observed synergetic or antagonistic effects. Radioadaptive response is one of the most significant factors which can be responsible for uncorrected radiation dose evaluation by biodosimetry methods. This phenomenon decreases effects of ionizing radiation approximately twice. Adaptive reaction can be induced by low radiation dose as well

  3. Study of 2-Iodo-3-( phenylsulfinyl)-2-propen-1-ol and its Analogues by Self-chemical Ionization Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Fang(张芳); ZHANG,Fang; GUO,Yin-Long (郭寅龙); GUO,Yin-Long; WEI,Qi(魏琦); WEI,Qi; MA,Sheng-Ming (麻生明); MA,Sheng-Ming

    2001-01-01

    Tne self-chemical ionization (SCI) in quadrupole mass spectrometry was developed to determine the structure of ( E)-2-iodo-3-( phenylslfinyl)-2-propen-1-ol and its 6 analogues.Some techniques that increase the sample quantity and heating speed and shorten vaporization time to obtain high pressure in the ion source were applied to increase the chance of ionmolecule reactions. Tne structures of these compounds were identified by mass spectral data of MH+ and stone characteristic fragment ions. Conpared with the mass spectra for 2-iodo-3-(phenylsulfinyl)-2-propen-1-ols obtained in electron impact ionization (EI), SCI showed more information, in particular, an improvement in amount of information at the high mass area. Tne absence of reagent gas makes the spectrumdean and sinple.

  4. Desorption electrospray ionization mass spectrometry in the analysis of chemical food contaminants in food

    NARCIS (Netherlands)

    Nielen, M.W.F.; Hooijerink, H.; Zomer, P.; Mol, J.G.J.

    2011-01-01

    Since its introduction, desorption electrospray ionization (DESI) mass spectrometry (MS) has been mainly applied in pharmaceutical and forensic analysis. We expect that DESI will find its way in many different fields, including food analysis. In this review, we summarize DESI developments aimed at c

  5. Screening of polycyclic polyprenylated acylphloroglucinols from Garcinia species using precursor ion discovery (PID) scan and ultra performance liquid chromatography electrospray ionization Q-TOF tandem mass spectrometry.

    Science.gov (United States)

    Zhou, Yan; Huang, Sheng-Xiong; Song, Jing-Zheng; Qiao, Chun-Feng; Li, Song-Lin; Han, Quan-Bin; Xu, Hong-Xi

    2009-10-01

    A strategy was newly developed to rapidly screen polycyclic polyprenylated acyl-phloroglucinols (PPAPs) from the plant matrices of nine Garcinia species using ultra-performance liquid chromatography (UPLC) coupled with comprehensive mass spectrometric approaches including precursor ion discovery (PID) and tandem mass (MS/MS) scans. The PPAPs share the same diagnostic product ion at m/z 177.02 in positive MS/MS scan, which may be increased as the base peak by ramping the cone voltage from 45 to 100 V. With this ramping cone voltage PID scan, it is feasible to selectively screen the PPAPs from 29 samples of nine Garcinia species. This approach has proven to be a powerful, highly selective, and sensitive tool for rapid screening and detection of nontargeted components in natural products before the purification and structural elucidation process. PMID:19643632

  6. Evaluation of matrix solid-phase dispersion extraction for 11 β-agonists in swine feed by liquid chromatography with electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Tao, Yanfei; Zhu, Fangwei; Chen, Dongmei; Xie, Shuyu; Yuanhu, Pan; Wang, Xu; Liu, Zhenli; Peng, Dapeng; Yuan, Zonghui

    2014-09-01

    A sensitive liquid chromatography with tandem mass spectrometry method was developed for the determination of 11 β-agonists (clenbuterol, salbutamol, ractopamine, terbutaline, fenoterol, cimaterol, isoxsuprine, mabuterol, mapenterol, clenproperol, and tulobuterol) in swine feed. This rapid, simple, and effective extraction method was based on matrix solid-phase dispersion. The limit of quantification of clenbuterol, cimaterol, mabuterol, salbutamol, terbutaline, mapenterol, clenproperol, and tulobuterol was 1 μg/kg and that of ractopamine, fenoterol, and isoxsuprine was 2 μg/kg. The recoveries of β-agonists spiked in swine feeds at a concentration range of 1-8 μg/kg were >83.1% with relative standard deviations <9.3%. This rapid and reliable method can be used to efficiently separate, characterize, and quantify the residues of 11 β-agonists in swine feeds with advantages of simple pretreatment and environmental friendliness. PMID:24981594

  7. Confirmation of phorate, terbufos, and their sulfoxides and sulfones in water by capillary gas chromatography/chemical ionization mass spectrometry

    International Nuclear Information System (INIS)

    A gas chromatographic/mass spectrometric method capable of confirming phorate, terbufos, their sulfoxides, and sulfones in water is reported. Parents and their metabolites are separated in less than 5 min using a short capillary GC column and high carrier gas linear velocities. Positive ion chemical ionization mass spectrometry generates (M + H) ions indicative of the different molecular weights of the analytes and at least one confirmatory fragment ion for each analyte. Residues have been qualitatively confirmed at the 1 ppb level in fortified water samples from a variety of sources. Apparent residues in control water were less than 0.1 ppb

  8. Synergistic effect of ionizing radiation on chemical disinfectant treatments for reduction of natural microflora on seafood

    Science.gov (United States)

    Kim, Hyunjoo; Ha, Ji-Hyoung; Lee, Ju-Woon; Jo, Cheorun; Ha, Sang-Do

    2012-08-01

    The purpose of this study was to determine whether combined treatments would produce synergistic disinfection effects on seafood products such as mussel and squid compared with single treatments. We investigated the bactericidal effects of chlorine and ionizing radiation on the natural microflora of mussel and squid. Total aerobic bacteria initially ranged from 102 to 104 Log CFU/g. More than 100 ppm of chlorine and irradiation at 1 kGy were sufficient to reduce the total aerobic bacteria on mussel and squid to a level lower than detection limit (10 CFU/g). Synergistic effects against natural microflora were observed for all combined treatment. These results suggest that a significant synergistic benefit results from combine chlorine-ionizing radiation treatment against natural microflora on mussel and squid.

  9. A novel automated hydrophilic interaction liquid chromatography method using diode-array detector/electrospray ionization tandem mass spectrometry for analysis of sodium risedronate and related degradation products in pharmaceuticals.

    Science.gov (United States)

    Bertolini, Tiziana; Vicentini, Lorenza; Boschetti, Silvia; Andreatta, Paolo; Gatti, Rita

    2014-10-24

    A simple, sensitive and fast hydrophilic interaction liquid chromatography (HILIC) method using ultraviolet diode-array detector (UV-DAD)/electrospray ionization tandem mass spectrometry was developed for the automated high performance liquid chromatography (HPLC) determination of sodium risedronate (SR) and its degradation products in new pharmaceuticals. The chromatographic separations were performed on Ascentis Express HILIC 2.7μm (150mm×2.1mm, i.d.) stainless steel column (fused core). The mobile phase consisted of formate buffer solution (pH 3.4; 0.03M)/acetonitrile 42:58 and 45:55 (v/v) for granules for oral solution and effervescent tablet analysis, respectively, at a flow-rate of 0.2mL/min, setting the wavelength at 262nm. Stability characteristics of SR were evaluated by performing stress test studies. The main degradation product formed under oxidation conditions corresponding to sodium hydrogen (1-hydroxy-2-(1-oxidopyridin-3-yl)-1-phosphonoethyl)phosphonate was characterized by high performance liquid chromatography-electrospray ionization-mass tandem mass spectrometry (HPLC-ESI-MS/MS). The validation parameters such as linearity, sensitivity, accuracy, precision and selectivity were found to be highly satisfactory. Linear responses were observed in standard and in fortified placebo solutions. Intra-day precision (relative standard deviation, RSD) was ≤1.1% for peak area and ≤0.2% for retention times (tR) without significant differences between intra- and inter-day data. Recovery studies showed good results for all the examined compounds (from 98.7 to 101.0%) with RSD ranging from 0.6 to 0.7%. The limits of detection (LOD) and quantitation (LOQ) were 1 and 3ng/mL, respectively. The high stability of standard and sample solutions at room temperature means an undoubted advantage of the method allowing the simultaneous preparation of many samples and consecutive chromatographic analyses by using an autosampler. The developed stability indicating

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

    Science.gov (United States)

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

    2015-07-01

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

  11. Liquid Chromatography with Electrospray Ionization and Tandem Mass Spectrometry Applied in the Quantitative Analysis of Chitin-Derived Glucosamine for a Rapid Estimation of Fungal Biomass in Soil.

    Science.gov (United States)

    Olofsson, Madelen A; Bylund, Dan

    2016-01-01

    This method employs liquid chromatography-tandem mass spectrometry to rapidly quantify chitin-derived glucosamine for estimating fungal biomass. Analyte retention was achieved using hydrophilic interaction liquid chromatography, with a zwitter-ionic stationary phase (ZIC-HILIC), and isocratic elution using 60% 5 mM ammonium formate buffer (pH 3.0) and 40% ACN. Inclusion of muramic acid and its chromatographic separation from glucosamine enabled calculation of the bacterial contribution to the latter. Galactosamine, an isobaric isomer to glucosamine, found in significant amounts in soil samples, was also investigated. The two isomers form the same precursor and product ions and could not be chromatographically separated using this rapid method. Instead, glucosamine and galactosamine were distinguished mathematically, using the linear relationships describing the differences in product ion intensities for the two analytes. The m/z transitions of 180 → 72 and 180 → 84 were applied for the detection of glucosamine and galactosamine and that of 252 → 126 for muramic acid. Limits of detection were in the nanomolar range for all included analytes. The total analysis time was 6 min, providing a high sample throughput method. PMID:26977151

  12. A simple and selective method for determination of phthalate biomarkers in vegetable samples by high pressure liquid chromatography-electrospray ionization-tandem mass spectrometry.

    Science.gov (United States)

    Zhou, Xi; Cui, Kunyan; Zeng, Feng; Li, Shoucong; Zeng, Zunxiang

    2016-06-01

    In the present study, solid-phase extraction cartridges including silica reversed-phase Isolute C18, polymeric reversed-phase Oasis HLB and mixed-mode anion-exchange Oasis MAX, and liquid-liquid extractions with ethyl acetate, n-hexane, dichloromethane and its mixtures were compared for clean-up of phthalate monoesters from vegetable samples. Best recoveries and minimised matrix effects were achieved using ethyl acetate/n-hexane liquid-liquid extraction for these target compounds. A simple and selective method, based on sample preparation by ultrasonic extraction and liquid-liquid extraction clean-up, for the determination of phthalate monoesters in vegetable samples by liquid chromatography/electrospray ionisation-tandem mass spectrometry was developed. The method detection limits for phthalate monoesters ranged from 0.013 to 0.120ngg(-1). Good linearity (r(2)>0.991) between MQLs and 1000× MQLs was achieved. The intra- and inter-day relative standard deviation values were less than 11.8%. The method was successfully used to determine phthalate monoester metabolites in the vegetable samples. PMID:26830597

  13. Validation of a liquid chromatography-electrospray ionization tandem mass spectrometric method to determine six polyether ionophores in raw, UHT, pasteurized and powdered milk.

    Science.gov (United States)

    Pereira, Mararlene Ulberg; Spisso, Bernardete Ferraz; Jacob, Silvana do Couto; Monteiro, Mychelle Alves; Ferreira, Rosana Gomes; Carlos, Betânia de Souza; da Nóbrega, Armi Wanderley

    2016-04-01

    This study aimed to validate a method developed for the determination of six antibiotics from the polyether ionophore class (lasalocid, maduramicin, monensin, narasin, salinomycin and semduramicin) at residue levels in raw, UHT, pasteurized and powdered milk using QuEChERS extraction and high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS). The validation was conducted under an in-house laboratory protocol that is primarily based on 2002/657/EC Decision, but takes in account the variability of matrix sources. Overall recoveries between 93% and 113% with relative standard deviations up to 16% were obtained under intermediate precision conditions. CCα calculated values did not exceed 20% the Maximum Residue Limit for monensin and 25% the Maximum Levels for all other substances. The method showed to be simple, fast and suitable for verifying the compliance of raw and processed milk samples regarding the limits recommended by Codex Alimentarius and those adopted in European Community for polyether ionophores. PMID:26593474

  14. Liquid Chromatography with Electrospray Ionization and Tandem Mass Spectrometry Applied in the Quantitative Analysis of Chitin-Derived Glucosamine for a Rapid Estimation of Fungal Biomass in Soil

    Directory of Open Access Journals (Sweden)

    Madelen A. Olofsson

    2016-01-01

    Full Text Available This method employs liquid chromatography-tandem mass spectrometry to rapidly quantify chitin-derived glucosamine for estimating fungal biomass. Analyte retention was achieved using hydrophilic interaction liquid chromatography, with a zwitter-ionic stationary phase (ZIC-HILIC, and isocratic elution using 60% 5 mM ammonium formate buffer (pH 3.0 and 40% ACN. Inclusion of muramic acid and its chromatographic separation from glucosamine enabled calculation of the bacterial contribution to the latter. Galactosamine, an isobaric isomer to glucosamine, found in significant amounts in soil samples, was also investigated. The two isomers form the same precursor and product ions and could not be chromatographically separated using this rapid method. Instead, glucosamine and galactosamine were distinguished mathematically, using the linear relationships describing the differences in product ion intensities for the two analytes. The m/z transitions of 180 → 72 and 180 → 84 were applied for the detection of glucosamine and galactosamine and that of 252 → 126 for muramic acid. Limits of detection were in the nanomolar range for all included analytes. The total analysis time was 6 min, providing a high sample throughput method.

  15. Comparison of rapid liquid chromatography-electrospray ionization-tandem mass spectrometry methods for determination of glycoalkaloids in transgenic field-grown potatoes.

    Science.gov (United States)

    Zywicki, Britta; Catchpole, Gareth; Draper, John; Fiehn, Oliver

    2005-01-15

    Two rapid methods for highly selective detection and quantification of the two major glycoalkaloids in potatoes, alpha-chaconine and alpha-solanine, were compared for robustness in high-throughput operations for over 1000 analytical runs using potato tuber samples from field trials. Glycoalkaloids were analyzed using liquid chromatography coupled to tandem mass spectrometry in multiple reaction monitoring mode. An electrospray interface was used in the detection of glycoalkaloids in positive ion mode. Classical reversed phase (RP) and hydrophilic interaction (HILIC) columns were investigated for chromatographic separation, ruggedness, recovery, precision, and accuracy. During the validation procedure both methods proved to be precise and accurate enough in relation to the high degree of endogenous biological variability found for field-grown potato tubers. However, the RP method was found to be more precise, more accurate, and, more importantly, more rugged than the HILIC method for maintaining the analytes' peak shape symmetry in high-throughput operation. When applied to the comparison of six classically bred potato cultivars to six genetically modified (GM) lines engineered to synthesize health beneficial inulins, the glycoalkaloid content in potato peels of all GM lines was found within the range of the six cultivars. We suggest complementing current unbiased metabolomic strategies by validating quantitative analytical methods for important target analytes such as the toxic glycoalkaloids in potato plants. PMID:15620882

  16. Liquid Chromatography with Post-Column Reagent Addition of Ammonia in Methanol Coupled to Negative Ion Electrospray Ionization Tandem Mass Spectrometry for Determination of Phenoxyacid Herbicides and their Degradation Products in Surface Water

    Directory of Open Access Journals (Sweden)

    Michele L. Etter

    2010-02-01

    Full Text Available A new liquid chromatography (LC-negative ion electrospray ionization (ESI–tandem mass spectrometry (MS/MS method with post-column addition of ammonia in methanol has been developed for the analysis of acid herbicides: 2,4-dichlorophenoxy ace- tic acid, 4-chloro-o-tolyloxyacetic acid, 2-(2-methyl-4-chlorophenoxybutyric acid, mecoprop, dichlorprop, 4-(2,4-dichlorophenoxy butyric acid, 2,4,5-trichlorophenoxy propionic acid, dicamba and bromoxynil, along with their degradation products: 4-chloro-2- methylphenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol and 3,5-dibromo-4-hydroxybenzoic acid. The samples were extracted from the surface water matrix using solid-phase extraction (SPE with a polymeric sorbent and analyzed with LC ESI- with selected reaction monitoring (SRM using a three-point confirmation approach. Chromatography was performed on a Zorbax Eclipse XDB-C18 (50 × 4.6 mm i.d., 1.8 µm with a gradient elution using water-methanol with 2 mM ammonium acetate mobile phase at a flow rate of 0.15 mL/min. Ammonia in methanol (0.8 M was added post-column at a flow rate of 0.05 mL/min to enhance ionization of the deg- radation products in the MS source. One SRM transition was used for quantitative analysis while the second SRM along with the ratio of SRM1/SRM2 within the relative standard deviation determined by standards for each individual pesticide and retention time match were used for confirmation. The standard deviation of ratio of SRM1/SRM2 obtained from standards run on the day of analysis for different phenoxyacid herbicides ranged from 3.9 to 18.5%. Limits of detection (LOD were between 1 and 15 ng L-1 and method detection limits (MDL with strict criteria requiring

  17. Highly sensitive and selective analysis of urinary steroids by comprehensive two-dimensional gas chromatography combined with positive chemical ionization quadrupole mass spectrometry

    OpenAIRE

    Zhang, Ying; Tobias, Herbert J.; Brenna, J. Thomas

    2012-01-01

    Comprehensive two dimensional gas chromatography (GC×GC) provides greater separation space than conventional GC. Because of fast peak elution, a time of flight mass spectrometer (TOFMS) is the usual structure-specific detector of choice. The quantitative capabilities of a novel GC×GC fast quadrupole MS were investigated with electron ionization (EI), and CH4 or NH3 positive chemical ionization (PCI) for analysis of endogenous urinary steroids targeted in anti-doping tests. Average precisions ...

  18. Quantification of levoglucosan and its isomers by High Performance Liquid Chromatography – Electrospray Ionization tandem Mass Spectrometry and its applications to atmospheric and soil samples

    Directory of Open Access Journals (Sweden)

    C. Piot

    2011-07-01

    Full Text Available The determination of atmospheric concentrations of levoglucosan and its two isomers, unambiguous tracers of biomass burning emissions, became even more important with the development of wood as renewable energy for domestic heating. Many researches demonstrated the increase during recent years of atmospheric particulate matter load due to domestic biomass combustion in developed countries. Analysis of biomass burning tracers is traditionally performed with Gas Chromatography-Mass Spectrometry (GC-MS technique after derivatization and requires an organic solvent extraction. A simpler and faster technique using Liquid Chromatography – Electrospray Ionisation – tandem Mass Spectrometry (LC-ESI-MS/MS was optimized for the analysis of levoglucosan, mannosan and galactosan isomers after an aqueous extraction. This technique allows a good separation between the three compounds in a very reduced time (runtime ~5 min. LOD and LOQ of this method are 30 μg l−1 and 100 μg l−1 respectively, allowing the use of filters from low-volume sampler (as commonly used in routine campaigns. A comparison of simultaneous levoglucosan measurements by GC-MS and LC-ESI-MS/MS for about 50 samples coming from different types of sampling sites and seasons was realized and shows very good agreement between the two methods. Therefore LC-ESI-MS/MS method can be used as an alternative to GC-MS particularly for measurement campaigns in routine where analysis time is important and detection limit is reduced. This paper shows that this method is also applicable to other environmental sample types like soil.

  19. Quantification of levoglucosan and its isomers by High Performance Liquid Chromatography – Electrospray Ionization tandem Mass Spectrometry and its applications to atmospheric and soil samples

    Directory of Open Access Journals (Sweden)

    N. Marchand

    2012-01-01

    Full Text Available The determination of atmospheric concentrations of levoglucosan and its two isomers, unambiguous tracers of biomass burning emissions, became even more important with the development of wood as renewable energy for domestic heating. Many researches demonstrated the increase during recent years of atmospheric particulate matter load due to domestic biomass combustion in developed countries. Analysis of biomass burning tracers is traditionally performed with Gas Chromatography-Mass Spectrometry (GC-MS technique after derivatization and requires an organic solvent extraction. A simpler and faster technique using Liquid Chromatography – Electrospray Ionisation – tandem Mass Spectrometry (LC-ESI-MS/MS was optimized for the analysis of levoglucosan, mannosan and galactosan isomers after an aqueous extraction. This technique allows a good separation between the three compounds in a very reduced time (runtime ~5 min. LOD and LOQ of this method are 30 μg l−1 and 100 μg l−1 respectively, allowing the use of filters from low-volume sampler (as commonly used in routine campaigns. A comparison of simultaneous levoglucosan measurements by GC-MS and LC-ESI-MS/MS for about 50 samples coming from different types of sampling sites and seasons was realized and shows very good agreement between the two methods. Therefore LC-ESI-MS/MS method can be used as an alternative to GC-MS particularly for measurement campaigns in routine where analysis time is important and detection limit is reduced. This paper shows that this method is also applicable to other environmental sample types like soil.

  20. Qualitative and quantitative analysis of polycyclic polyprenylated acylphloroglucinols from Garcinia species using ultra performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

    Science.gov (United States)

    Zhou, Yan; Lee, Stephanie; Choi, Franky Fung Kei; Xu, Gang; Liu, Xin; Song, Jing-Zheng; Li, Song-Lin; Qiao, Chun-Feng; Xu, Hong-Xi

    2010-09-23

    Polycyclic polyprenylated acylphloroglucinols (PPAPs) are a group of natural products isolated from different Garcinia species with a wide range of important biological activities. In this study, an ultra performance liquid chromatography (UPLC) coupled to photodiode-array detection and quadrupole time-of-flight mass spectrometry (Q-TOF) method was developed to characterize 16 PPAPs in 10 Garcinia species. In source dissociation techniques based on cone voltage fragmentation were used to fragment the deprotonated molecules and multiple mass spectrometry (MS/MS) using ramping collision energy were used to further break down the resulting product ions. The resulting characteristic fragment ions were generated by cleavage of C1-C5 bond and C7-C8 bond through concerted pericyclic reaction, which is especially valuable for differentiating three types of PPAPs isomers. As such, two new PPAPs isomers present in minor amount in the extracts of Garcinia oblongifolia were tentatively characterized by comparing their tandem mass spectra to the known ones. In addition, an UPLC-Q-TOF-MS method was validated for the quantitative determination of PPAPs. The method exhibited limits of detection from 2.7 to 21.4 ng mL(-1) and intra-day and inter-day variations were less than 3.7% and the recovery was in the range of 89-107% with RSD less than 9.0%. This UPLC-Q-TOF-MS method has successfully been applied to quantify 16 PPAPs in 32 samples of 10 Garcinia species, which were found to be a rich source of PPAPs. PMID:20869510

  1. Determination of nine sensitizing disperse dyes in activated sludge by ultrasound-assisted liquid-liquid extraction-ultra-performance liquid chromatography-electrospray ionization-tandem mass spectrometry.

    Science.gov (United States)

    Zhou, Linjun; Shi, Lili; Liu, Jining; Lv, Fenglan; Xu, Yanhua

    2016-01-01

    A method was developed on the basis of ultrasound-assisted liquid-liquid extraction ultra-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (ULLE-UPLC-ESI-MS/MS) to determine nine sensitizing disperse dyes in activated sludge. The samples were extracted using ULLE and separated through UPLC on an ACQUITY UPLCTM BEH C18 column with a gradient elution program of acetonitrile and acidified water (containing 2% acetonitrile, 0.2% formic acid, and 0.005 mol/L ammonium; pH 2.7) as the mobile phase. The samples were then identified and quantified through UPLC-ESI-MS/MS in a positive mode and multiple reaction monitoring. Results showed good linearity (10-1000 μg/L, 0.9934-0.9998), detection limit (0.08-2.17 μg/L), and quantification limit (0.27-7.38 μg/L) for the nine sensitizing disperse dyes, with recoveries ranging from 65.0 to 111.3%. The proposed method was applied to detect and determine the concentration of sensitizing disperse dyes in sludge samples obtained from various sewage treatment plants (six dyeing enterprises and one dye manufacturer). Three sensitizing disperse dyes were identified, and the lowest concentration detected was 10 μg/kg. PMID:26521175

  2. Metabolites identification of harmane in vitro/in vivo in rats by ultra-performance liquid chromatography combined with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

    Science.gov (United States)

    Li, Shuping; Liu, Wei; Teng, Liang; Cheng, Xuemei; Wang, Zhengtao; Wang, Changhong

    2014-04-01

    Harmane, a β-carboline alkaloid with a wide spectrum of pharmacological activities, is naturally present in the human diet, in numerous foodstuffs and in hallucinogenic plants such as Peganum harmala, Banisteriopsis caapi and Tribulus terrestris. However, the precise metabolic fate of harmane remains unknown. In order to know whether harmane is extensively metabolized, a rapid and sensitive method using ultra-performance liquid chromatography combined with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (UPLC/ESI-QTOF-MS) was used to analyze the metabolic profile of harmane in vitro and in vivo in rats. A total of 21 metabolites were identified from the rat liver microsomes and rat liver S9 (9), rat urine (11), feces (16), bile (16), and plasma (10) after a single oral administration of harmane using MetaboLynx™ and MassFragment ™ software tools. It indicated that the biliary and faecal clearance were the major excretion routes for harmane as well as its metabolites. The specific CLogP values combined with different acidic and alkaline mobile phase were helpful and useful for distinguishing N-oxidation and monohydroxylation metabolites. The metabolic transformation pathways of harmane included monohydroxylation, dihydroxylation, N-oxidation, O-glucuronide conjugation, O-sulphate conjugation, and glutathione conjugation. In conclusion, this study showed an insight into the metabolism of harmane. PMID:24486683

  3. Can Edman degradation be used for quantification? Isotope-dilution liquid chromatography-electrospray ionization tandem mass spectrometry and the long-term stability of 20 phenylthiohydantoin-amino acids.

    Science.gov (United States)

    Satoh, Ryo; Goto, Takaaki; Lee, Seon Hwa; Oe, Tomoyuki

    2013-10-01

    Edman degradation is a well-known method for obtaining amino acid (AA) sequences from a peptide by means of sequential reactions that release the N-terminal AAs from the peptide as a phenylthiohydantoin (PTH) derivative. Because of unexpected loss during the reaction and handling, there are few reports of use of this reaction for quantification. This manuscript describes the development of isotope-dilution liquid chromatography-electrospray ionization tandem mass spectrometry for 20 PTH-AA derivatives, and long-term stability testing of PTH-AAs to ensure quantitative quality in the reaction. The 20 corresponding [(13)C6]-PTH-AAs were prepared by use of a one-pot reaction involving a mixture of [(13)C6]-Edman reagent and 20 AAs. Good linearity was observed for standard curves for the PTH-AAs, using the corresponding [(13)C6]-PTH-AAs as internal standards (1-100 pmol per injection, r(2) = 0.989-1.000). Serum albumin (human), pepsin (porcine stomach mucosa), α-casein (bovine milk), ribonuclease A (bovine), lysozyme (chicken egg white), and insulin (bovine) subjected to Edman degradation were examined as model proteins and peptides for N-terminal AA analysis. The results of the impurity test were satisfactory. Yield from the entire reaction with human serum albumin was estimated to be at least 75%, indicating great potential for absolute quantification of proteins without protein standards. PMID:23545858

  4. Synergistic effect of ionizing radiation on chemical disinfectant treatments for reduction of natural microflora on seafood

    International Nuclear Information System (INIS)

    The purpose of this study was to determine whether combined treatments would produce synergistic disinfection effects on seafood products such as mussel and squid compared with single treatments. We investigated the bactericidal effects of chlorine and ionizing radiation on the natural microflora of mussel and squid. Total aerobic bacteria initially ranged from 102 to 104 Log CFU/g. More than 100 ppm of chlorine and irradiation at 1 kGy were sufficient to reduce the total aerobic bacteria on mussel and squid to a level lower than detection limit (10 CFU/g). Synergistic effects against natural microflora were observed for all combined treatment. These results suggest that a significant synergistic benefit results from combine chlorine-ionizing radiation treatment against natural microflora on mussel and squid. - Highlights: ► Synergistic effect of combined treatments of chlorine and irradiation was tested using seafood. ► Synergistic effect against natural microflora was observed for all combined treatments. ► Therefore, it is recommended that industry use the combined treatment for better effect.

  5. Chemical derivatization for electrospray ionization mass spectrometry. 1. Alkyl halides, alcohols, phenols, thiols, and amines

    Energy Technology Data Exchange (ETDEWEB)

    Quirke, J.M.E.; Adams, C.L.; Van Berkel, G.J. (Oak Ridge National Lab., TN (United States))

    1994-04-15

    Derivatization strategies and specific derivatization reactions for conversion of simple alkyl halides, alcohols, phenols, thiols, and amines to ionic or solution-ionizable derivatives, that is [open quotes]electrospray active[close quotes] (ES-active) forms of the analyte, are presented. Use of these reactions allows detection of analytes among those listed that are not normally amenable to analysis by electrospray ionization mass spectrometry (ES-MS). In addition, these reactions provide for analysis specificity and flexibility through functional group specific derivatization and through the formation of derivatives that can be detected in positive ion or in negative ion mode. For a few of the functional groups, amphoteric derivatives are formed that can be analyzed in either positive or negative ion modes. General synthetic strategies for transformation of members of these five compound classes to ES-active species are presented along with illustrative examples of suitable derivatives. Selected derivatives were prepared using model compounds and the ES mass spectra obtained for these derivatives are discussed. The analytical utility of derivatization for ES-MS analysis is illustrated in three experiments: (1) specific detection of the major secondary alcohol in oil of peppermint, (2) selective detection of phenols within a synthetic mixture of phenols, and (3) identification of the medicinal amines within a commercially available cold medication as primary, secondary or tertiary. 65 refs., 3 figs., 3 tabs.

  6. Non-linear effects in the determination of paleotemperature U37(k') alkenone ratios by chemical ionization mass spectrometry.

    Science.gov (United States)

    Chaler, R; Villanueva, J; Grimalt, J O

    2003-09-12

    The performance of gas chromatography coupled to mass spectrometry in the positive chemical ionization mode using ammonia as reagent gas (GC-PCI-MS) in the analysis of C37 alkenones for paleotemperature estimation has been re-evaluated. In some conditions, the discrepancies observed in the measurement of the U37(k') index with this technique as compared with GC equipped with flame ionization detection (GC-FID) cannot be explained by differences in sensitivity between the tri- and diunsaturated alkenones. Thus, at low (currently 0.4) U37(k') values the GC-PCI-MS determinations may be observed to be lower or higher, respectively, than those measured with GC-FID. As shown by analysis of a series of synthetic C37 alkenone standards these discrepant results can be explained by non linear effects in the GC-PCI-MS response factors. Second-order polynomial functions provide equations that describe better the signal to amount of analyte ratios. Users of GC-PCI-MS should calibrate their instruments with standards of known C37 alkenone composition in order to minimize non-linear effects. PMID:14509345

  7. Pulsed Chemical Oxygen Iodine Lasers Excited by Pulse Gas Discharge with the Assistance of Surface Sliding Discharge Pre-ionization

    International Nuclear Information System (INIS)

    Continuous-wave chemical oxygen-iodine lasers (COILs) can be operated in a pulsed operation mode to obtain a higher peak power. The key point is to obtain a uniform and stable glow discharge in the mixture of singlet delta oxygen and iodide. We propose using an electrode system with the assistance of surface sliding pre-ionization to solve the problem of the stable glow discharge with a large aperture. The pre-ionization unit is symmetrically fixed on the plane of the cathode surface. A uniform and stable glow discharge is obtained in a mixture of iodide (such as CH3I) and nitrogen at the specific deposition energy of 4.5 J/L, pressure of 1.99–3.32 kPa, aperture size of 11 cm × 10 cm. The electrode system is applied in a pulsed COIL. Laser energy up to 4.4 J is obtained and the specific energy output is 2 J/L. (fundamental areas of phenomenology(including applications))

  8. Gas Chromatography Coupled to Atmospheric Pressure Chemical Ionization FT-ICR Mass Spectrometry for Improvement of Data Reliability.

    Science.gov (United States)

    Schwemer, Theo; Rüger, Christopher P; Sklorz, Martin; Zimmermann, Ralf

    2015-12-15

    Atmospheric pressure chemical ionization (APCI) offers the advantage of molecular ion information with low fragmentation. Hyphenating APCI to gas chromatography (GC) and ultrahigh resolution mass spectrometry (FT-ICR MS) enables an improved characterization of complex mixtures. Data amounts acquired by this system are very huge, and existing peak picking algorithms are usually extremely time-consuming, if both gas chromatographic and ultrahigh resolution mass spectrometric data are concerned. Therefore, automatic routines are developed that are capable of handling these data sets and further allow the identification and removal of known ionization artifacts (e.g., water- and oxygen-adducts, demethylation, dehydrogenation, and decarboxylation). Furthermore, the data quality is enhanced by the prediction of an estimated retention index, which is calculated simply from exact mass data combined with a double bond equivalent correction. This retention index is used to identify mismatched elemental compositions. The approach was successfully tested for analysis of semivolatile components in heavy fuel oil and diesel fuel as well as primary combustion particles emitted by a ship diesel research engine. As a result, 10-28% of the detected compounds, mainly low abundant species, classically assigned by using only the mass spectrometric information, were identified as not valid and removed. Although GC separation is limited by the slow acquisition rate of the FT-ICR MS (<1 Hz), a database driven retention time comparison, as commonly used for low resolution GC/MS, can be applied for revealing isomeric information. PMID:26560682

  9. Comparative analysis of different plant oils by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    Science.gov (United States)

    Jakab, Annamaria; Héberger, Károly; Forgács, Esther

    2002-11-01

    Different vegetable oil samples (almond, avocado, corngerm, grapeseed, linseed, olive, peanut, pumpkin seed, soybean, sunflower, walnut, wheatgerm) were analyzed using high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry. A gradient elution technique was applied using acetone-acetonitrile eluent systems on an ODS column (Purospher, RP-18e, 125 x 4 mm, 5 microm). Identification of triacylglycerols (TAGs) was based on the pseudomolecular ion [M+1]+ and the diacylglycerol fragments. The positional isomers of triacylglycerol were identified from the relative intensities of the [M-RCO2]+ fragments. Linear discriminant analysis (LDA) as a common multivariate mathematical-statistical calculation was successfully used to distinguish the oils based on their TAG composition. LDA showed that 97.6% of the samples were classified correctly. PMID:12462617

  10. Quantitative determination of terbutaline and orciprenaline in human plasma by gas chromatography/negative ion chemical ionization/mass spectrometry.

    Science.gov (United States)

    Leis, H J; Gleispach, H; Nitsche, V; Malle, E

    1990-06-01

    A method for the determination of unconjugated terbutaline and orciprenaline in human plasma is described. The assay is based on stable isotope dilution gas chromatography/negative ion chemical ionization/mass spectrometry. An inexpensive and rapid method for preparation of stable isotope labelled analogues as well as their use in quantitative gas chromatography/mass spectrometry is shown. A highly efficient sample work-up procedure with product recoveries of more than 95% is presented. The method developed permits quantitative measurement of terbutaline and orciprenaline in human plasma down to 100 pg ml-1, using 1 ml of sample. Plasma levels of terbutaline after oral administration of 5 mg of terbutaline sulphate were estimated. PMID:2357489

  11. Quantitative analysis of methadone in biological fluids using deuterium-labeled methadone and GLC-chemical-ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Hackey, D.L. (Argonne National Lab., IL); Kreek, M.J.; Mattson, D.H.

    1977-11-01

    The (+)-, (-)-, and (+-)-/sup 2/H/sub 5/-methadones, which contained five deuterium atoms in one aromatic ring, were synthesized for use in clinical pharmacological studies and as internal standards. GLC--chemical-ionization mass spectrometry was used to determine plasma and urinary methadone levels by an inverse isotope dilution assay. Plasma drug levels could be determined to 10 pmoles/ml, and urine levels could be measured to 5 pmoles/ml. Plasma methadone levels were examined in several patients undergoing methadone maintenance therapy. These levels generally ranged between 100 and 400 ng/ml (320 to 1300 pmoles/ml) after an average oral dose of 1 mg/kg/day. The methadone half-life was 28.8 +- 4.8 hr.

  12. Primary Ion Depletion Kinetics (PIDK Studies as a New Tool for Investigating Chemical Ionization Fragmentation Reactions with PTR-MS.

    Directory of Open Access Journals (Sweden)

    Erna Schuhfried

    Full Text Available We report on a new approach for studying fragmentation channels in Proton Transfer Reaction-Mass Spectrometry (PTR-MS, which we name primary ion depletion kinetics (PIDK. PTR-MS is a chemical ionization mass spectrometric (CIMS technique deploying hydronium ions for the chemical ionization. Induced by extremely high concentrations of analyte M, depletion of the primary ions in the drift tube occurs. This is observed as quasi zero concentration of the primary ion H3O(+, and constant MH(+. Under these non-standard conditions, we find an overall changed fragmentation. We offer two explanations. Either the changed fragmentation pattern is the result of secondary proton transfer reactions. Or, alternatively, the fast depletion of H3O(+ leads to reduced heating of H3O(+ in the drift field, and consequently changed fragmentation following protonation of the analyte M. In any case, we use the observed changes in fragmentation as a successful new approach to fragmentation studies, and term it primary ion depletion kinetics, PIDK. PIDK easily yields an abundance of continuous data points with little deviation, because they are obtained in one experimental run, even for low abundant fragments. This is an advantage over traditional internal kinetic energy variation studies (electric field per number density (E/N variation studies. Also, some interpretation on the underlying fragmentation reaction mechanisms can be gleamed. We measure low occurring fragmentation (<2% of MH(+ of the compounds dimethyl sulfide, DMS, a compound that reportedly does not fragment, diethyl sulfide DES, and dipropyl sulfide DPS. And we confirm and complement the results with traditional E/N studies. Summing up, the new approach of primary ion depletion kinetics allows for the identification of dehydrogenation [MH(+ -H2] and adduct formation (RMH(+ as low abundant fragmentation channels in monosulfides.

  13. Phospholipidomic identification of potential serum biomarkers in dengue fever, hepatitis B and hepatitis C using liquid chromatography-electrospray ionization-tandem mass spectrometry.

    Science.gov (United States)

    Khedr, Alaa; Hegazy, Maha A; Kammoun, Ahmed K; Shehata, Mostafa A

    2016-01-15

    The serum phospholipid (PL) profiles of healthy volunteers (HE) and patients with recently diagnosed dengue fever (DF), hepatitis B (HBV), and hepatitis C (HCV) were investigated using liquid chromatography-ion trap-mass spectrometry (LC-IT-MS) and liquid chromatography-triple quad-mass spectrometry (LC-TQ-MS). Major PLs, including lyso-phosphatidylcholins (LPCs), phosphatidylcholins (PCs), phosphatidylinositols (PIs), phosphatidylethanolamines (PEs) and phosphatidylserines (PSs), were characterized in human serum using LC-IT-MS. Thirty-five PLs were quantified using seven non-endogenous odd-carbon PL standards. An MS search protocol for the identification of PLs is described. The analytical method was optimized to achieve maximum recovery and detection. PLs were detected with minimal ionization suppression. The PLs species were characterized on the basis of (i) MS(2) peaks due to polar head, (ii) precursor ion or neutral loss scans, (iii) identification of fatty acid, (iv) identification of sn-1 and sn-2 fatty acid. The quantitation data were subjected to principal component analysis (PCA), and a significant difference was observed between the PL profiles of the investigated diseases and those of HE subjects. The significance of the changes in each lipid among the four groups was statistically assessed using one-way analysis of variance (ANOVA) followed by Bonferroni post hoc multiple comparison. The serum profiles of 28 PLs were determined to be significantly different and enabled the discrimination between HE individuals and the studied patients. Potentially dysregulated PLs were considered as differentiating biomarkers to diagnose DF, HBV, and HCV. PMID:26708624

  14. Protocol for an electrospray ionization tandem mass spectral product ion library: development and application for identification of 240 pesticides in foods.

    Science.gov (United States)

    Zhang, Kai; Wong, Jon W; Yang, Paul; Hayward, Douglas G; Sakuma, Takeo; Zou, Yunyun; Schreiber, André; Borton, Christopher; Nguyen, Tung-Vi; Kaushik, Banerjee; Oulkar, Dasharath

    2012-07-01

    Modern determination techniques for pesticides must yield identification quickly with high confidence for timely enforcement of tolerances. A protocol for the collection of liquid chromatography (LC) electrospray ionization (ESI)-quadruple linear ion trap (Q-LIT) mass spectrometry (MS) library spectra was developed. Following the protocol, an enhanced product ion (EPI) library of 240 pesticides was developed by use of spectra collected from two laboratories. A LC-Q-LIT-MS workflow using scheduled multiple reaction monitoring (sMRM) survey scan, information-dependent acquisition (IDA) triggered collection of EPI spectra, and library search was developed and tested to identify the 240 target pesticides in one single LC-Q-LIT MS analysis. By use of LC retention time, one sMRM survey scan transition, and a library search, 75-87% of the 240 pesticides were identified in a single LC/MS analysis at fortified concentrations of 10 ng/g in 18 different foods. A conventional approach with LC-MS/MS using two MRM transitions produced the same identifications and comparable quantitative results with the same incurred foods as the LC-Q-LIT using EPI library search, finding 1.2-49 ng/g of either carbaryl, carbendazim, fenbuconazole, propiconazole, or pyridaben in peaches; carbendazim, imazalil, terbutryn, and thiabendazole in oranges; terbutryn in salmon; and azoxystrobin in ginseng. Incurred broccoli, cabbage, and kale were screened with the same EPI library using three LC-Q-LIT and a LC-quadruple time-of-flight (Q-TOF) instruments. The library search identified azoxystrobin, cyprodinil, fludioxinil, imidacloprid, metalaxyl, spinosyn A, D, and J, amd spirotetramat with each instrument. The approach has a broad application in LC-MS/MS type targeted screening in food analysis. PMID:22686274

  15. The Temperature Structure in Ionized Nebulae and the Chemical Evolution of Galaxies

    OpenAIRE

    2002-01-01

    A few results that indicate the presence of temperature variations in gaseous nebulae are reviewed. The evidence is based on: a) temperatures derived from different methods, and b) on comparisons of abundances predicted by models of galactic chemical evolution with abundances derived from observations.

  16. Analytical model of chemical phase and formation of DSB in chromosomes by ionizing radiation

    Czech Academy of Sciences Publication Activity Database

    Barilla, J.; Lokajíček, Miloš; Pisaková, Hana; Šimr, P.

    2013-01-01

    Roč. 36, č. 1 (2013), s. 11-17. ISSN 0158-9938 Institutional support: RVO:68378271 Keywords : radiobiological mechanism * chemical phase * DSB formation * oxygen effect Subject RIV: BF - Elementary Particles and High Energy Physics Impact factor: 0.848, year: 2013

  17. Natural products in Glycyrrhiza glabra (licorice) rhizome imaged at the cellular level by atmospheric pressure matrix-assisted laser desorption/ionization tandem mass spectrometry imaging

    DEFF Research Database (Denmark)

    Li, Bin; Bhandari, Dhaka Ram; Janfelt, Christian;

    2014-01-01

    .02 Da. With a mass resolving power of 140 000 and a bin width of 5 ppm in the image processing, the two compounds were well resolved in full-scan mode, and appeared with different distributions in the tissue sections. The identities of the compounds and their distributions were validated in a subsequent...... saponins in legume species, combing the spatially resolved chemical information with morphological details at the microscopic level. Furthermore, the technique offers a scheme capable of high-throughput profiling of metabolites in plant tissues....

  18. Chemical Analysis of Organic Aerosols Using Reactive Nanospray Desorption Electrospray Ionization Mass Spectrometry

    Science.gov (United States)

    Laskin, A.; Laskin, J.; Nizkorodov, S.

    2013-12-01

    Nanospray Desorption Electrospray Ionization (nano-DESI) technique integrated with high resolution mass spectrometry (HR-MS) enables molecular level analysis of organic aerosol (OA) samples. In nano-DESI, analyte is desorbed into a small volume solvent bridge formed between two capillaries positioned in contact with analyte and enables fast and efficient characterization of OA collected on substrates without sample preparation. We report applications of the nano-DESI/HR-MS approach in a number of our recent studies focused on molecular identification of organic compounds in laboratory and in field collected OA samples. Reactive nano-DESI approach where selected reagent is added to the solvent is used for examining the presence of individual species containing specific functional groups and for their quantification within complex mixtures of OA. Specifically, we use the Girard's reagent T (GT) to probe and quantify carbonyl compounds in the SOA mixtures. We estimate for the first time the amounts of dimers and trimers in the SOA mixtures. We found that the most abundant dimer in limonene/O3 SOA was detected at the ˜0.5 pg level and the total amount of dimers and trimers in the analyzed sample was ˜11 pg. Understanding of the OA composition at the molecular level allowed us to identify key aging reactions, including the transformation of carbonyls to imines and carbonyl-imine oligomerization, that may contribute to the formation of brown carbon in the atmosphere.

  19. Online monitoring of chemical reactions by polarization-induced electrospray ionization.

    Science.gov (United States)

    Meher, Anil Kumar; Chen, Yu-Chie

    2016-09-21

    Polarization-induced electrospray ionization (PI-ESI) is a simple technique for instant generation of gas-phase ions directly from a microliter-sized droplet for mass spectrometric analysis. A sample droplet was placed over a dielectric substrate and in proximity (2-3 mm) to the inlet of a mass spectrometer. Owing to the polarization effect induced by the high electric field provided by the mass spectrometer, the droplet was polarized and the electrospray was generated from the apex of the droplet. The polarization-induced electrospray could last for tens of seconds, which was sufficiently long to monitor fast reactions occurring within few seconds. Thus, we demonstrated the feasibility of using the droplet-based PI-ESI MS for the online monitoring of fast reactions by simply mixing two droplets (5-10 μL) containing reactants on a dielectric substrate placed in front of a mass spectrometer applied with a high voltage (-4500 V). Schiff base reactions and oxidation reactions that can generate intermediates/products within a few seconds were selected as the model reactions. The ionic reaction species generated from intermediates and products can be simultaneously monitored by PI-ESI MS in real time. We also used this approach to selectively detect acetone from a urine sample, in which acetone was derivatized in situ. In addition, the possibility of using this approach for quantitative analysis of acetone from urine samples was examined. PMID:27590551

  20. Chemical chaperones reduce ionizing radiation-induced endoplasmic reticulum stress and cell death in IEC-6 cells

    International Nuclear Information System (INIS)

    Highlights: • UPR activation precedes caspase activation in irradiated IEC-6 cells. • Chemical ER stress inducers radiosensitize IEC-6 cells. • siRNAs that targeted ER stress responses ameliorate IR-induced cell death. • Chemical chaperons prevent cell death in irradiated IEC-6 cells. - Abstract: Radiotherapy, which is one of the most effective approaches to the treatment of various cancers, plays an important role in malignant cell eradication in the pelvic area and abdomen. However, it also generates some degree of intestinal injury. Apoptosis in the intestinal epithelium is the primary pathological factor that initiates radiation-induced intestinal injury, but the mechanism by which ionizing radiation (IR) induces apoptosis in the intestinal epithelium is not clearly understood. Recently, IR has been shown to induce endoplasmic reticulum (ER) stress, thereby activating the unfolded protein response (UPR) signaling pathway in intestinal epithelial cells. However, the consequences of the IR-induced activation of the UPR signaling pathway on radiosensitivity in intestinal epithelial cells remain to be determined. In this study, we investigated the role of ER stress responses in IR-induced intestinal epithelial cell death. We show that chemical ER stress inducers, such as tunicamycin or thapsigargin, enhanced IR-induced caspase 3 activation and DNA fragmentation in intestinal epithelial cells. Knockdown of Xbp1 or Atf6 with small interfering RNA inhibited IR-induced caspase 3 activation. Treatment with chemical chaperones prevented ER stress and subsequent apoptosis in IR-exposed intestinal epithelial cells. Our results suggest a pro-apoptotic role of ER stress in IR-exposed intestinal epithelial cells. Furthermore, inhibiting ER stress may be an effective strategy to prevent IR-induced intestinal injury

  1. Chemical chaperones reduce ionizing radiation-induced endoplasmic reticulum stress and cell death in IEC-6 cells

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Eun Sang; Lee, Hae-June; Lee, Yoon-Jin [Division of Radiation Effects, Korea Institute of Radiological and Medical Sciences, Seoul 139-706 (Korea, Republic of); Jeong, Jae-Hoon [Division of Radiotherapy, Korea Institute of Radiological and Medical Sciences, Seoul 139-706 (Korea, Republic of); Kang, Seongman [Division of Life Sciences, Korea University, Seoul 136-701 (Korea, Republic of); Lim, Young-Bin, E-mail: yblim@kirams.re.kr [Division of Radiation Effects, Korea Institute of Radiological and Medical Sciences, Seoul 139-706 (Korea, Republic of)

    2014-07-25

    Highlights: • UPR activation precedes caspase activation in irradiated IEC-6 cells. • Chemical ER stress inducers radiosensitize IEC-6 cells. • siRNAs that targeted ER stress responses ameliorate IR-induced cell death. • Chemical chaperons prevent cell death in irradiated IEC-6 cells. - Abstract: Radiotherapy, which is one of the most effective approaches to the treatment of various cancers, plays an important role in malignant cell eradication in the pelvic area and abdomen. However, it also generates some degree of intestinal injury. Apoptosis in the intestinal epithelium is the primary pathological factor that initiates radiation-induced intestinal injury, but the mechanism by which ionizing radiation (IR) induces apoptosis in the intestinal epithelium is not clearly understood. Recently, IR has been shown to induce endoplasmic reticulum (ER) stress, thereby activating the unfolded protein response (UPR) signaling pathway in intestinal epithelial cells. However, the consequences of the IR-induced activation of the UPR signaling pathway on radiosensitivity in intestinal epithelial cells remain to be determined. In this study, we investigated the role of ER stress responses in IR-induced intestinal epithelial cell death. We show that chemical ER stress inducers, such as tunicamycin or thapsigargin, enhanced IR-induced caspase 3 activation and DNA fragmentation in intestinal epithelial cells. Knockdown of Xbp1 or Atf6 with small interfering RNA inhibited IR-induced caspase 3 activation. Treatment with chemical chaperones prevented ER stress and subsequent apoptosis in IR-exposed intestinal epithelial cells. Our results suggest a pro-apoptotic role of ER stress in IR-exposed intestinal epithelial cells. Furthermore, inhibiting ER stress may be an effective strategy to prevent IR-induced intestinal injury.

  2. 液相色谱-串联质谱法测定保健食品中维生素B12%Determination of vitamin B12 in function foods by liquid chromatography electrospray ionization tandem mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    林宏琳; 华永有; 黄宏南

    2011-01-01

    目的 建立测定保健食品中维生素B12的液相色谱-串联质谱法.方法 样品添加内标人参皂苷Re溶液,固相萃取法( SPE)对试样进行富集、净化,以甲醇(A)和纯水(B)为流动相经Bio Basic-18 PIONEER柱(150 mm×2.1 mm,5μm)梯度洗脱分离,串联离子阱质谱在电喷雾电离正离子(ESI+)-全扫描(full)-二级质谱(MS/MS)模式下按内标法测定.结果 维生素B12在50~500 ng/ml范围内具有良好的线性,相关系数r=0.992,回收率75.2% ~ 89.5%,精密度3.6%~5.9%,检出限为5 ng/g,定量限为16 ng/g.结论本法可应用于保健食品的检测或产品质量控制.%Objective To establish a method of determining vitamin B12 in health food products by liquid chromatography electrospray ionization tandem mass spectrometry (LC-MS/MS). Methods After mixing samples with internal standard solution of ginsenoside Re, the mixtures of samples were extracted by solid phase extraction, and separated on a Bio Basic-18 PIONEER column (ISO mm ×2. 1 mm, 5 u.m) by a mobile phase of methanol ( A) + water ( B) with the gradient elution program. Detection was carried out by a liquid chromatography coupled electrospray ionization and ion trap mass spectrometry with ESI + , MS/MS and full scan mode. Results Calibration curve was linear within the range of 50-SOOng/ml with a correlation coefficient of more than 0. 99; the limit of detection ( LOD) was 5 ng/g and the limit of quantification ( LOQ) was 16 ng/g. The extraction recoveries were 75.2%-88.5%, RSDs were 3.6% -5.9%. Conclusion This method could meet the requirements of domestic and international laws and regulations, and could be used in the determination of VBI2 in health food products or for the quality control of the products.

  3. Tandem accelerators

    International Nuclear Information System (INIS)

    After the installation of Ti-acceleration tubes and substantial modifications and additions to the EN tandem accelerator the performance of the machine has stabilized. The voltage behaviour of the tubes obviously improves as conditioning times necessary to run up to 6 MV decrease. A gridded lens has been added at the entrance of the first acceleration tube, and a second foil stripper is now installed in the short dead section between the high-energy tubes. The MP tandem also has been running stably during most of the year. However, beam instabilities originating from the last tube section and wear problems at the low-energy set of pelletron-chains caused some loss of beam time. During the fall, one set of pelletron charging chains has to be replaced after 49,000 hours of operation. In the course of the year, the MP and the EN tandem accelerators finished their 100,000th and 150,000th hours of operations, respectively. Preparations for the installation of the 3 MV negative heavy ion injector for the MP are progressing steadily. External beam transport, terminal ion optics, and data acquisition and control systems are to a major extent completed; the integration of the terminal power supplies has started. After the final assembly of the accelerator column structure, first voltage runs can be performed. (orig.)

  4. Evaluation of sensitivity for positive tone non-chemically and chemically amplified resists using ionized radiation: EUV, x-ray, electron and ion induced reactions

    Science.gov (United States)

    Oshima, Akihiro; Oyama, Tomoko Gowa; Washio, Masakazu; Tagawa, Seiichi

    2013-03-01

    The different exposure sources induce a different energy deposition in resist materials. Linear energy transfer (LET) effect for resist sensitivity is very important issue from the viewpoint of radiation induced chemical reactions for high-volume nanofabrication. The sensitivities of positive tone non-chemically (non-CA, ZEP) and chemically amplified (CA, UV-3) resist materials are evaluated using various ionized radiation such as EUV, soft X-rays, EB and various ion beams. Since the notations of sensitivity of resist vary with exposure sources, in order to evaluate systematically, the resist sensitivity were estimated in terms of absorbed dose in resist materials. Highly-monochromated EUV and soft X-rays (6.7 nm - 3.1 nm) from the BL27SU of the SPring-8, high energy ion beams (C6+, Ne10+, Mg12+, Si14+ , Ar18+, Kr36+ and Xe54+) with 6 MeV/u from MEXP of HIMAC, EB from low energy EB accelerator (Hamamatsu Photonics, EB-engine®, 100 kV) and EB lithography system (30 keV and 75keV) were used for the exposure. For non-CA and CA resist materials, it was found that LET effects for sensitivity would be hardly observed except for heavier ion beams. Especially, in the case of the high energy ion beam less than Si14+ with 6 MeV/u, it is suggested that the radiation induced chemical reaction would be equivalent to EUV, soft X-ray and EB exposure. Hence, it indicates that the resist sensitivity could be systematically evaluated by absorbed dose in resist materials.

  5. Use of electron ionization and atmospheric pressure chemical ionization in gas chromatography coupled to time-of-flight mass spectrometry for screening and identification of organic pollutants in waters.

    Science.gov (United States)

    Portolés, Tania; Mol, Johannes G J; Sancho, Juan V; Hernández, Félix

    2014-04-25

    A new approach has been developed for multiclass screening of organic contaminants in water based on the use of gas chromatography coupled to hybrid quadrupole high-resolution time-of-flight mass spectrometry with atmospheric pressure chemical ionization (GC-(APCI)QTOF MS). The soft ionization promoted by the APCI source allows effective and wide-scope screening based on the investigation of the molecular ion and/or protonated molecule. This is in contrast to electron ionization (EI) where ionization typically results in extensive fragmentation, and diagnostic ions and/or spectra need to be known a priori to facilitate detection of the analytes in the raw data. Around 170 organic contaminants from different chemical families were initially investigated by both approaches, i.e. GC-(EI)TOF and GC-(APCI)QTOF, including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and a notable number of pesticides and relevant metabolites. The new GC-(APCI)QTOF MS approach easily allowed widening the number of compounds investigated (85 additional compounds), with more pesticides, personal care products (UV filters, musks), polychloronaphthalenes (PCNs), antimicrobials, insect repellents, etc., most of them considered as emerging contaminants. Both GC-(EI)TOF and GC-(APCI)QTOF methodologies have been applied, evaluating their potential for a wide-scope screening in the environmental field. PMID:24674644

  6. Quantification of new antiepileptic drugs by liquid chromatography/electrospray ionization tandem mass spectrometry and its application to cellular uptake experiment using human placental choriocarcinoma BeWo cells.

    Science.gov (United States)

    Furugen, Ayako; Kobayashi, Masaki; Nishimura, Ayako; Takamura, Shigeo; Narumi, Katsuya; Yamada, Takehiro; Iseki, Ken

    2015-10-01

    A method for quantification of new antiepileptic drugs, including lamotrigine (LTG), levetiracetam (LEV), gabapentin (GBP), and topiramate (TPM), in cellular samples, using liquid chromatography/electrospray ionization tandem mass spectrometry was developed to better understand the membrane transport mechanisms of these drugs. Cell lysate was deproteinized by methanol containing LEV-d3 as an internal standard (IS). Chromatographic separation was performed on a C18 column using gradient elution with methanol-water-formic acid (10:90:0.1, v/v/v) and methanol-formic acid (100:0.1, v/v). Analytes were detected in positive ion electrospray mode with selected reaction monitoring (SRM). This method was applicable for a linear range of 5 to 500pmol for LTG; 5 to 1000pmol for LEV; 10 to 10,000pmol for GBP; and 5 to 5000pmol for TPM. The intra-day precision, inter-day precision, and accuracy data were assessed and found to be acceptable. This developed and validated method was then successfully applied to the investigation of uptake of the new antiepileptic drugs in placental choriocarcinoma BeWo cells. The intracellular concentration of these drugs in BeWo cells, accumulating over 30min at 37°C was in the order of GBP>LTG>LEV≈TPM. Furthermore, the uptake of GBP at 4°C was much lower than that at 37°C. The uptake of GBP was saturated at high concentrations. The kinetic parameters calculated for GBP uptake in BeWo cells were determined as Km of 105.4±6.4μM and Vmax at 8153±348pmol/mg protein/min. The novel method described here should enable investigators to elucidate the transport mechanisms of these antiepileptic drugs in BeWo cells. PMID:26343016

  7. Identification and comparative proteomic study of quail and duck egg white protein using 2-dimensional gel electrophoresis and matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometry analysis.

    Science.gov (United States)

    Hu, S; Qiu, N; Liu, Y; Zhao, H; Gao, D; Song, R; Ma, M

    2016-05-01

    A proteomic study of egg white proteins from 2 major poultry species, namely quail (Coturnix coturnix) and duck (Anas platyrhynchos), was performed with comparison to those of chicken (Gallus gallus) through 2-dimensional polyacrylamide gel electrophoresis (2-DE) analysis. By using matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometry (MALDI-TOF MS/MS), 29 protein spots representing 10 different kinds of proteins as well as 17 protein spots designating 9 proteins were successfully identified in quail and duck egg white, respectively. This report suggested a closer relationship between quail and chicken egg white proteome patterns, whereas the duck egg white protein distribution on the 2-DE map was more distinct. In duck egg white, some well-known major proteins, such as ovomucoid, clusterin, extracellular fatty acid-binding protein precursor (ex-FABP), and prostaglandin D2 synthase (PG D2 synthase), were not detected, while two major protein spots identified as "deleted in malignant brain tumors 1" protein (DMBT1) and vitellogenin-2 were found specific to duck in the corresponding range on the 2-DE gel map. These interspecies diversities may be associated with the egg white protein functions in cell defense or regulating/supporting the embryonic development to adapt to the inhabiting environment or reproduction demand during long-term evolution. The findings of this work will give insight into the advantages involved in the application on egg white proteins from various egg sources, which may present novel beneficial properties in the food industry or related to human health. PMID:26957635

  8. Improving detection sensitivity of amino acids in thyroid tissues by using phthalic acid as a mobile phase additive in hydrophilic interaction chromatography-electrospray ionization-tandem mass spectrometry

    International Nuclear Information System (INIS)

    Highlights: • HILIC–ESI-MS/MS method was used to quantify 24 free AAs in human thyroid tissues. • Addition of 0.08 mM of phthalic acid to the eluent enhanced the sensitivity of AAs. • Narrowed peak shapes of AAs were achieved with phthalic acid in the mobile phase. • The mechanism for the signal intensity enhancement by phthalic acid was investigated. - Abstract: In this work, 0.08 mmol L−1 of phthalic acid was introduced as a mobile phase additive to quantify free amino acids (AAs) by hydrophilic interaction liquid chromatography (HILIC) coupled with electrospray ionization tandem mass spectrometry (ESI-MS/MS). The addition of phthalic acid significantly increased the signal intensity of protonated AA ions, resulting from the decrease of the relative abundance of AA sodium adducts. Meanwhile, the chromatographic peak shapes of AAs were optimized. As a consequence, there was a noticeable increase in the sensitivity of detection for AAs. The limits of detection (LOD) and quantification (LOQ) of the AAs ranged from 0.0500 to 20.0 ng mL−1 and from 0.100 to 50.0 ng mL−1, respectively, which were 4–50 times lower compared to the values measured without the addition of phthalic acid. The enhanced detection and separation of AAs were obtained by merely adding phthalic acid to the mobile phase without changing other conditions. Eventually, this simple method was validated and successfully applied to the analysis of twenty-four kinds of free AAs in human thyroid carcinoma and para-carcinoma tissues, demonstrating a significant increase of most AAs in thyroid carcinoma tissues (p < 0.05)

  9. Improving detection sensitivity of amino acids in thyroid tissues by using phthalic acid as a mobile phase additive in hydrophilic interaction chromatography-electrospray ionization-tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Wanshu [National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032 (China); Guan, Qing [Department of Head and Neck Surgery, Fudan University Shanghai Cancer Center (FUSCC), Shanghai 200032 (China); Department of Oncology, Shanghai Medical College, Fudan University, Shanghai 200032 (China); Sun, Tuanqi, E-mail: tuanqisun@163.com [Department of Head and Neck Surgery, Fudan University Shanghai Cancer Center (FUSCC), Shanghai 200032 (China); Department of Oncology, Shanghai Medical College, Fudan University, Shanghai 200032 (China); Cao, Yanjing [National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032 (China); Zhang, Li, E-mail: zhangli7488@sioc.ac.cn [National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032 (China); Guo, Yinlong, E-mail: ylguo@sioc.ac.cn [National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032 (China)

    2015-04-22

    Highlights: • HILIC–ESI-MS/MS method was used to quantify 24 free AAs in human thyroid tissues. • Addition of 0.08 mM of phthalic acid to the eluent enhanced the sensitivity of AAs. • Narrowed peak shapes of AAs were achieved with phthalic acid in the mobile phase. • The mechanism for the signal intensity enhancement by phthalic acid was investigated. - Abstract: In this work, 0.08 mmol L{sup −1} of phthalic acid was introduced as a mobile phase additive to quantify free amino acids (AAs) by hydrophilic interaction liquid chromatography (HILIC) coupled with electrospray ionization tandem mass spectrometry (ESI-MS/MS). The addition of phthalic acid significantly increased the signal intensity of protonated AA ions, resulting from the decrease of the relative abundance of AA sodium adducts. Meanwhile, the chromatographic peak shapes of AAs were optimized. As a consequence, there was a noticeable increase in the sensitivity of detection for AAs. The limits of detection (LOD) and quantification (LOQ) of the AAs ranged from 0.0500 to 20.0 ng mL{sup −1} and from 0.100 to 50.0 ng mL{sup −1}, respectively, which were 4–50 times lower compared to the values measured without the addition of phthalic acid. The enhanced detection and separation of AAs were obtained by merely adding phthalic acid to the mobile phase without changing other conditions. Eventually, this simple method was validated and successfully applied to the analysis of twenty-four kinds of free AAs in human thyroid carcinoma and para-carcinoma tissues, demonstrating a significant increase of most AAs in thyroid carcinoma tissues (p < 0.05)

  10. Quantification of 3α-hydroxytibolone in human plasma by high performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS: Application in a bioequivalence study in healthy postmenopausal volunteers

    Directory of Open Access Journals (Sweden)

    Lucas Azevedo Portela

    2016-06-01

    Full Text Available A sensitive, specific and fast method to quantify 3α-hydroxytibolone in human plasma using deuterated 3α-hydroxytibolone (d5 as internal standard is described. The analyte and the internal standard were extracted from plasma (900 μL by liquid-liquid extraction using ethyl ether/hexane (50/50, v/v and ammonium hydroxide (50%. The extracts were analyzed by high performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry without derivatization. Chromatography was performed isocratically on a Gemini-NX™ C18 5 μm (150 × 4.6 mm i. d. column. The method had a chromatographic run time of 3.75 min and a linear calibration curve over the range 1–100 ng/mL. The limit of quantification validated was 1 ng/mL. This method was used to assess the bioequivalence between two different tibolone oral formulations: Livolon (1.25 mg tablet provided by Biolab Sanus Farmacêutica (Brazil, as the test formulation, and Libiam™ (1.25 mg tablet produced by Libbs Farmacêutica (Brazil, as the reference formulation. A single 3.75 mg dose of each formulation was administered to 46 postmenopausal female healthy volunteers. The study was conducted in an open, randomized, two-period crossover balanced design with a 2 week washout interval between the doses. The 90% confidence interval for Cmax, AUC(0-last and AUC(0-inf individual test/reference ratios were 97.48–111.51, 95.35–103.20 and 96.42–103.86, respectively. It is concluded that Livolon (1.25 mg tablet is bioequivalent to Libiam™ (1.25 mg tablet, with regards to both rate and extent of absorption.

  11. Characterization of the variation in the imidazole alkaloid profile of Pilocarpus microphyllus in different seasons and parts of the plant by electrospray ionization mass spectrometry fingerprinting and identification of novel alkaloids by tandem mass spectrometry.

    Science.gov (United States)

    Abreu, Iika N; Mazzafera, Paulo; Eberlin, Marcos N; Zullo, Marco António T; Sawaya, Alexandra C H F

    2007-01-01

    Pilocarpus microphyllus (Rutaceae), popularly known as jaborandi, is the only commercial source of an imidazole alkaloid named pilocarpine. In the present study, the variation in the profile of imidazole alkaloids in different seasons and in different parts of the P. microphyllus plant during the summer was analyzed by electrospray ionization mass spectrometry in the positive ion mode [ESI(+)-MS]. The fingerprints of these extracts repeatedly presented similar ions which were mass-selected and studied by tandem mass spectrometry (ESI-MS/MS and ESI-MS/MS/MS) and high-resolution mass spectrometry, resulting in the characterization of eight imidazole alkaloids. The data from the ESI(+)-MS fingerprints were analyzed by principal component analysis (PCA), showing that pilocarpine was present mainly in the summer, whereas in the autumn mainly pilosine and winter anhydropilosine were found. Three alkaloids, reported for the first time in extracts of P. microphyllus, were found. Analysis of the distribution of alkaloids in different parts of the plant during the summer showed that, although pilocarpine was present throughout the plant, 13-nor-8(11)-dihydropilocarpine was found mainly in the stem, pilosine and anhydropilosine were present mainly in the intermediary leaves, and the three new alkaloids were mainly found in the leaflets and petioles. Based on the dissociation patterns of these alkaloids, we observed that there were three structurally related groups of alkaloids differing in their distribution in the plant tissues and responding differently to seasonal variations. These results also indicate that these three groups of alkaloids could belong to intermediate, parallel or competitive pathways for pilocarpine formation biosynthesis. PMID:17330216

  12. Rapid and simultaneous analysis of ten aromatic amines in mainstream cigarette smoke by liquid chromatography/electrospray ionization tandem mass spectrometry under ISO and "Health Canada intensive" machine smoking regimens.

    Science.gov (United States)

    Xie, Fuwei; Yu, Jingjing; Wang, Sheng; Zhao, Ge; Xia, Qiaoling; Zhang, Xiaobing; Zhang, Shusheng

    2013-10-15

    Ten primary aromatic amines (AAs) in mainstream cigarette smoke under both ISO and "Health Canada intensive" machine smoking regimens were determined in this work, which were suspected to be carcinogenic compounds. The measured AAs included aniline, ortho-toluidine, meta-toluidine, para-toluidine, 1-naphthylamine, 2-naphthylamine, 3-aminobiphenyl, 4-aminobiphenyl, meta-phenylenediamine and meta-anisidine. For rapidly and sensitively analyzing these AAs, a liquid chromatography-electrospray ionization tandem mass spectrometric (LC-MS/MS) method coupled with solid phase extraction (SPE) was developed. The particulate phase of mainstream cigarette smoke was collected on a Cambridge filter pads, while the gas phase was trapped by 25 mL 5% HCl solution. Then, the pad was extracted in an ultrasonic bath with the impinger HCl solution. After being neutralized with NaOH, the extract was purified with a HLB solid phase extraction column, and then was analyzed with LC-MS/MS using isotope-labeled internal standard. The overall sample pretreatment and analysis time was less than 1.5h. The limits of detection for all targets ranged from 0.05 ng cig(-1) to 0.96 ng cig(-1) with the recoveries in the range of 75.0-131.8%. And the intra-day and inter-day precisions were less than 10% and 16%, respectively. Under HCI machine smoking regimen, the AAs yields in mainstream cigarette smoke were much higher and the average increases were greater than 100% compared with those under ISO smoking condition. PMID:24054615

  13. Liquid chromatography-electrospray ionization tandem mass spectrometry for on-line characterization, monitoring and isotopic profiling of the main selenium-metabolite in human urine after consumption of Se-rich and Se-enriched food

    International Nuclear Information System (INIS)

    The metabolism of selenium (Se) in the human body has yet not completely been unravelled and hence, an efficient method for characterization and on-line monitoring of the main Se-compound in human urine after consumption of Se-rich food was developed. Total Se-concentration in human urine after consumption of several Se-rich products was measured with inductively coupled plasma mass spectrometry (ICP-MS). The highest Se concentration in urine was observed after 4-10 h. The urine samples were brought onto a reversed phase column and the Se was detected by ICP-MS. Parameters for liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS) measurements were optimized by using commercially available sugars, because it is known that some of the urinary metabolites contain a sugar moiety. In order to characterize the predominant Se-metabolite, it was necessary to extensively clean-up the sample and preconcentrate the species. The main metabolite was measured on its precursor ion on three different m/z according to three isotopes of Se. Relative peak surfaces matched the relative abundances of the isotopes. The product ions could be measured in a human urine sample in accordance to the product ions of the commercially available sugars. Moreover, the evidence of a selenosugar was demonstrated by the use of the Se-isotopes when measuring the product ions. LC-ESI-MS-MS was proven to be very efficient for the characterization of the main urinary Se-metabolite and can be used for on-line monitoring of the compound in urine samples. The method can be extended for clinical screening after consumption of Se-(en)rich(ed) food by use of the Se-isotopic profile and/or of the typical product ions of (methyl)-N-acetyl-hexosamines

  14. Comparison of the rationale used in setting occupational exposure standards for ionizing radiation and hazardous chemical substances

    International Nuclear Information System (INIS)

    Ten chemicals which create significant occupational hazard are reviewed. They are toluene diisocyanate, hydrogen fluoride, n-hexane, carbon disulphide, cadmium, inorganic mercury, cobalt, nitroglycerol, silica and vinyl chloride. Each is discussed under the headings of physiological intake and elimination in humans, characteristics of acute and chronic toxicity, sites of occupational exposure and rationale for limits of such exposure. Since radioactive substances yield ionizing radiation as the common hazard the treatment of the current permissible levels of exposure is somewhat simpler. Having set out industrial standards for exposure to hazardous substances and radionuclides, a detailed comparison is made. Exposure limits to ioninzing radiation are sufficiently low to remove the appearance of directly related injury. It is expected however that low level exposure may have a stochastic effect, that is, there is the possibility of a slightly increased incidence of neoplasms in a large exposed population, but numbers will be too small to be able to attribute any particular case to the exposure. TLVs on the other hand, depending on the particular chemical, may be high enough in the workplace to permit some directly related signs or symptoms in the exposed individual. 244 refs

  15. The Use of Atmospheric Pressure Chemical Ionization Mass Spectrometry with High Performance Liquid Chromatography and Other Separation Techniques for Identification of Triacylglycerols

    Czech Academy of Sciences Publication Activity Database

    Řezanka, Tomáš; Sigler, Karel

    2007-01-01

    Roč. 3, - (2007), s. 252-271. ISSN 1573-4110 R&D Projects: GA ČR GA203/06/0219 Institutional research plan: CEZ:AV0Z50200510 Keywords : triacylglycerols * atmospheric presssure chemical ionization * mass spectrometry Subject RIV: EE - Microbiology, Virology Impact factor: 1.815, year: 2007

  16. Validation of a qualitative screening method for pesticides in fruits and vegetables by gas chromatography quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization

    NARCIS (Netherlands)

    Portoles, T.; Mol, J.G.J.; Sancho, J.V.; Lopez, F.J.; Hernandez, F.

    2014-01-01

    A wide-scope screening method was developed for the detection of pesticides in fruit and vegetables. The method was based on gas chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer with an atmospheric pressure chemical ionization source (GC-(APCI)QTOF MS). A non-target acq

  17. Physical, chemical, microbiological and sensorial behaviour evolution of non cooked pressed cheese paste while in refrigerated storage, made with red chilli powder, treated by heat or ionization

    International Nuclear Information System (INIS)

    The evolution of different physical, chemical, microbiological and sensorial characteristics of a Tunisian manufactured cheese made of non cooked pressed cheese paste with red chilli powder treated by heat, was measured while in refrigerated storage and compared to the one treated by ionization (author)

  18. Qualitative analysis of some carboxylic acids by ion-exclusion chromatography with atmospheric pressure chemical ionization mass spectrometric detection.

    Science.gov (United States)

    Helale, Murad I H; Tanaka, Kazuhiko; Taoda, Hiroshi; Hu, Wenzhi; Hasebe, Kiyoshi; Haddad, Paul R

    2002-05-17

    A simple, selective and sensitive method for the determination of carboxylic acids has been developed. A mixture of formic, acetic, propionic, valeric, isovaleric, isobutyric, and isocaproic acids has been separated on a polymethacrylate-based weak acidic cation-exchange resin (TSK gel OA pak-A) based on an ion-exclusion chromatographic mechanism with detection using UV-photodiode array, conductivity and atmospheric pressure chemical ionization mass spectrometry (APCI-MS). A mobile phase consisting of 0.85 mM benzoic acid in 10% aqueous methanol (pH 3.89) was used to separate the above carboxylic acids in about 40 min. For LC-MS, the APCI interface was used in the negative ionization mode. Linear plots of peak area versus concentration were obtained over the range 1-30 mM (r2=0.9982) and 1-30 mM (r2=0.9958) for conductimetric and MS detection, respectively. The detection limits of the target carboxylic acids calculated at S/N=3 ranged from 0.078 to 2.3 microM for conductimetric and photometric detection and from 0.66 to 3.82 microM for ion-exclusion chromatography-APCI-MS. The reproducibility of retention times was 0.12-0.16% relative standard deviation for ion-exclusion chromatography and 1.21-2.5% for ion-exclusion chromatography-APCI-MS. The method was applied to the determination of carboxylic acids in red wine, white wine, apple vinegar, and Japanese rice wine. PMID:12108651

  19. Study of physical, chemical and structural effects caused by ionizing radiation and preservation on human costal cartilage

    International Nuclear Information System (INIS)

    Tissue Banks around the world have stored human cartilages obtained from cadaver donors for use in several kinds of reconstructive surgeries. To ensure that such tissues are not contaminated, they have been sterilized with ionizing radiation. However, high doses of gamma radiation may cause undesirable changes in the tissues, decreasing the mechanical properties of the grafts. In this work, we evaluate physical/chemical and structural changes in deep-frozen (-70 deg C) or high concentration of glycerol (> 98%) preserved costal cartilage, before and after sterilization by ionizing radiation at 3 different doses (15, 25 and 50 kGy). Samples of human costal cartilage were obtained from 20 cadaver donors ranging between 18 and 55 years old. A 60Co irradiator was used as irradiation source. Thermogravimetry (TG), Optical Coherence Tomography (OCT) and mechanical tension and compression tests were carried out to evaluate the changes in the cartilage. Regarding the thermogravimetric results, the obtained data has shown that the TG curves have the same pattern independently of the sample irradiated or not. On the other hand, non-irradiated samples showed great variability of thermogravimetric curves among different donors and for the same donor. Concerning the mechanical tests, when cartilages were irradiated with 15 kGy, their mechanical strength to tension was increased about 24%, in both deep-froze and preserved in glycerol samples. Samples deep-frozen, when irradiated with 25 and 50 kGy, presented a decrease of their mechanical behavior smaller than those preserved in high concentrations of glycerol and irradiated with the same dose. Therefore, deep-frozen cartilages can be sterilized with doses until 50 kGy and cartilages preserved in high concentrations of glycerol can be sterilized with doses until 25 kGy without significant changes in their bio-mechanical properties.(author)

  20. Structural Characterization and Identification of Major Constituents in Jitai Tablets by High-Performance Liquid Chromatography/Diode-Array Detection Coupled with Electrospray Ionization Tandem Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Weidong Zhang

    2012-09-01

    Full Text Available In the present study a universally applicable HPLC-DAD/ESI-MS/MS method was developed for carrying out the comprehensive characterization of Jitai tablets (JTT. Based on the ESI-MSn fragmentation patterns of the reference standards, a total of 101 components were identified or tentatively characterized by comparing their retention times, UV and MS spectra with those of reference standards or through the matching of empirical information with those of published components in the in-house library. The characteristic fragmentation pattern of alkaloids, phenolic acids, tanshinones, flavonoid glycosides, cyanogenic glycosides, ginsenosides, 2-(2-phenylethyl chromones, phthalides and gingerol-related compounds were tentatively elucidated using structurally-relevant product ions. It was observed that neutral losses of C9H10O3 and C9H8O2 were the characteristic product ions of scopola alkaloids. Neutral fragment mandelonitrile was the characteristic ion of cyanogenic glycosides. To our knowledge, tropylium ion and C4H2O unit were the characteristic ions of 2-(2-phenylethyl chromone, which resulted from the Retro-Diels-Alder (RDA cleavage of the C ring. The results indicated that the developed analysis method could be employed as a rapid, effective technique for structural characterization of chemical constituents in TCM. This work is expected to provide comprehensive information for the quality evaluation and pharmacokinetic studies of JTT.

  1. Simultaneous chemical fingerprint and quantitative analysis of Rhizoma Smilacis Glabrae by accelerated solvent extraction and high-performance liquid chromatography with tandem mass spectrometry.

    Science.gov (United States)

    Dai, Weiquan; Zhao, Weiquan; Gao, Fangyuan; Shen, Jingjing; Lv, Diya; Qi, Yunpeng; Fan, Guorong

    2015-05-01

    Rhizoma Smilacis Glabrae (RSG) is a well-known herbal medicine with the homology of medicine and food. In this study, simultaneous chemical fingerprint and quantitative analysis of the bioactive flavonoid components of RSG were developed using accelerated solvent extraction and high-performance liquid chromatography coupled with ion trap tandem mass spectrometry. The operational parameters of accelerated solvent extraction including extraction solvent, extraction temperature, static extraction time, solid-to-liquid ratio, and extraction cycles were optimized. Hierarchical cluster analysis, similarity analysis, and principal component analysis were performed to evaluate the similarity and variation of the samples collected from several provinces in China. Subsequently, high-performance liquid chromatography fingerprints were established for the discrimination of 16 batches of RSG samples, and the major six flavonoids, namely, toxifolin, neoastilbin, astilbin, neoisoastilbin, isoastilbin, and engeletin were then quantitatively determined. The calibration curves for all the six analytes showed good linearity (r(2) > 0.999), and the limits of detection and quantification were less than 0.10 and 0.27 μg·mL(-1) , respectively. Therefore, the proposed extraction and determination methods were proved to be robust and reliable for the quality control of RSG. PMID:25678068

  2. Novel characterisation of minor α-linolenic acid isomers in linseed oil by gas chromatography and covalent adduct chemical ionisation tandem mass spectrometry.

    Science.gov (United States)

    Gómez-Cortés, P; Brenna, J T; Lawrence, P; de la Fuente, M A

    2016-06-01

    Discrimination between polyunsaturated fatty acid isomers with three double bonds is a great challenge, due to structural similarities and similar polarities. In this study, we report the identification of four minor geometrical isomers of α-linolenic acid (ALA) present in linseed oil samples: (9E,12Z,15E)-, (9Z,12Z,15E)-, (9Z,12E,15Z)- and (9E,12Z,15Z)-octadeca-9,12,15-trienoic acids, chromatographically resolved by gas chromatography (GC) using a new and highly polar ionic phase column (SLB-IL111). Gas chromatography-electron ionisation mass spectrometry (GC-EIMS) determined that the four unknown compounds were C18:3 n-3 isomers. The positional 9-12-15 C18:3 configuration was achieved by covalent adduct chemical ionisation tandem mass spectrometry (CACI-MS/MS) while geometrical configuration was established with analytical standards based on relative retention. We hypothesised that these isomers are formed during linseed oil deodorisation and postulate preferred and unfavoured isomerisation pathways of ALA. PMID:26830571

  3. Simultaneous determination of 16 brominated flame retardants in food and feed of animal origin by fast gas chromatography coupled to tandem mass spectrometry using atmospheric pressure chemical ionisation.

    Science.gov (United States)

    Bichon, E; Guiffard, I; Vénisseau, A; Lesquin, E; Vaccher, V; Brosseaud, A; Marchand, P; Le Bizec, B

    2016-08-12

    A gas chromatography tandem mass spectrometry method using atmospheric pressure chemical ionisation was developed for the monitoring of 16 brominated flame retardants (7 usually monitored polybromodiphenylethers (PBDEs) and BDE #209 and 8 additional emerging and novel BFRs) in food and feed of animal origin. The developed analytical method has decreased the run time by three compared to conventional strategies, using a 2.5m column length (5% phenyl stationary phase, 0.1mm i.d., 0.1μmf.t.), a pulsed split injection (1:5) with carrier gas helium flow rate at 0.48mLmin(-1) in one run of 20 min. For most BFRs, analytical data were compared with the current analytical strategy relying on GC/EI/HRMS (double sector, R=10000 at 10% valley). Performances in terms of sensitivity were found to meet the Commission recommendation (118/2014/EC) for nBFRs. GC/APCI/MS/MS represents a promising alternative for multi-BFRs analysis in complex matrices, in that it allows the monitoring of a wider list of contaminants in a single injection and a shorter run time. PMID:27425757

  4. Airborne intercomparison of HOx measurements using laser-induced fluorescence and chemical ionization mass spectrometry during ARCTAS

    Directory of Open Access Journals (Sweden)

    J. H. Crawford

    2012-08-01

    Full Text Available The hydroxyl (OH and hydroperoxyl (HO2 radicals, collectively called HOx, play central roles in tropospheric chemistry. Accurate measurements of OH and HO2 are critical to examine our understanding of atmospheric chemistry. Intercomparisons of different techniques for detecting OH and HO2 are vital to evaluate their measurement capabilities. Three instruments that measured OH and/or HO2 radicals were deployed on the NASA DC-8 aircraft throughout Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS in the spring and summer of 2008. One instrument was the Penn State Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS for OH and HO2 measurements based on Laser-Induced Fluorescence (LIF spectroscopy. A second instrument was the NCAR Selected-Ion Chemical Ionization Mass Spectrometer (SI-CIMS for OH measurement. A third instrument was the NCAR Peroxy Radical Chemical Ionization Mass Spectrometer (PeRCIMS for HO2 measurement. Formal intercomparison of LIF and CIMS was conducted for the first time on a same aircraft platform. The three instruments were calibrated by quantitative photolysis of water vapor by ultraviolet (UV light at 184.9 nm with three different calibration systems. The absolute accuracies were ±32% (2σ for the LIF instrument, ±65% (2σ for the SI-CIMS instrument, and ±50% (2σ for the PeRCIMS instrument. In general, good agreement was obtained between the CIMS and LIF measurements of both OH and HO2 measurements. Linear regression of the entire data set yields [OH]CIMS = 0.89 × [OH]LIF + 2.8 × 104 cm−3 with a correlation coefficient r2 = 0.72 for OH, and [HO2]CIMS = 0.86 × [HO2]LIF + 3.9 parts per trillion by volume (pptv, equivalent to pmol mol−1 with a correlation coefficient r2 = 0.72 for HO2. In general, the difference between CIMS and LIF instruments for OH and HO2 measurements can be explained by their combined measurement uncertainties. Comparison with box model results shows some

  5. Airborne intercomparison of HOx measurements using laser-induced fluorescence and chemical ionization mass spectrometry during ARCTAS

    Directory of Open Access Journals (Sweden)

    G. Chen

    2012-03-01

    Full Text Available The hydroxyl (OH and hydroperoxyl (HO2 radicals, collectively called HOx, play central roles in tropospheric chemistry. Accurate measurements of OH and HO2 are critical to examine our understanding of atmospheric chemistry. Intercomparisons of different techniques for detecting OH and HO2 are vital to evaluate their measurement capabilities. Three instruments that measured OH and/or HO2 radicals were deployed on the NASA DC-8 aircraft throughout Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS, in the spring and summer of 2008. One instrument was the Penn State Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS for OH and HO2 measurements based on Laser-Induced Fluorescence (LIF spectroscopy. A second instrument was the NCAR Selected-Ion Chemical Ionization Mass Spectrometer (SI-CIMS for OH measurement. A third instrument was the NCAR Peroxy Radical Chemical Ionization Mass Spectrometer (PeRCIMS for HO2 measurement. Formal intercomparison of LIF and CIMS was conducted for the first time on a same aircraft platform. The three instruments were calibrated by quantitative photolysis of water vapor by UV light at 184.9 nm with three different calibration systems. The absolute accuracies were ±32% (2σ for the LIF instrument, ±65% (2σ for the SI-CIMS instrument, and ±50% (2σ for the PeRCIMS instrument. In general, good agreement was obtained between the CIMS and LIF measurements of both OH and HO2 measurements. Linear regression of the entire data set yields [OH]CIMS = 0.89 × [OH]LIF + 2.8 × 105 cm−3 with a correlation coefficient, r2 = 0.72 for OH and [HO2]CIMS = 0.86 × [HO2]LIF + 3.9 parts per trillion by volume (pptv, equivalent to pmol mol−1 with a correlation coefficient, r2 = 0.72 for HO2. In general, the difference between CIMS and LIF instruments for OH and HO2 measurements can be explained by their combined measurement uncertainties. Comparison with box model results shows some

  6. Young stars and ionized nebulae in M83: comparing chemical abundances at high metallicity

    CERN Document Server

    Bresolin, Fabio; Urbaneja, Miguel A; Gieren, Wolfgang; Ho, I-Ting; Pietrzynski, Grzegorz

    2016-01-01

    We present spectra of 14 A-type supergiants in the metal-rich spiral galaxy M83. We derive stellar parameters and metallicities, and measure a spectroscopic distance modulus m-M = 28.47 +\\- 0.10 (4.9 +\\- 0.2 Mpc), in agreement with other methods. We use the stellar characteristic metallicity of M83 and other systems to discuss a version of the galaxy mass-metallicity relation that is independent of the analysis of nebular emission lines and the associated systematic uncertainties. We reproduce the radial metallicity gradient of M83, which flattens at large radii, with a chemical evolution model, constraining gas inflow and outflow processes. We carry out a comparative analysis of the metallicities we derive from the stellar spectra and published HII region line fluxes, utilizing both the direct, Te-based method and different strong-line abundance diagnostics. The direct abundances are in relatively good agreement with the stellar metallicities, once we apply a modest correction to the nebular oxygen abundance...

  7. Protection against genetic hazards from environmental chemical mutagens: experience with ionizing radiation

    International Nuclear Information System (INIS)

    In radiation protection, the recurrent theme is, and always has been, dose limitation whether it is for occupational workers, individual members of the public or the population as a whole. The key words are 'dose' and 'limitation'. The quantitative system of dose limitation has been achieved because of a number of conceptual developments in our understanding of the mechanism of radiation action, development of radiation dosimetry, the accumulation of a vast body of quantitative information on dose-effect relationships and the effects of various biological and physical variables that affect these relationships of data on patterns and levels of exposures likely to be encountered to make estimates of the effects expected to result from such exposures, and balancing of risks to society against the benefits derived, the latter a matter of informed judgement. The philosophy has always been to avoid all unnecessary exposures and to limit the necessary exposures (justified by the benefits expected) to as low a level as reasonably achievable, social and economic factors being taken into acccount. The introduction of the concept that the system of dose limitation to the population should be based on genetic risks has stressed the need for careful planning to ensure that our genetic heritage is not endangered. Transfer of this knowledge to the field of chemical protection is discussed. (Auth.)

  8. Biological Effects of Ionizing Radiation

    Science.gov (United States)

    Ingram, M.; Mason, W. B.; Whipple, G. H.; Howland, J. W.

    1952-04-07

    This report presents a review of present knowledge and concepts of the biological effects of ionizing radiations. Among the topics discussed are the physical and chemical effects of ionizing radiation on biological systems, morphological and physiological changes observed in biological systems subjected to ionizing radiations, physiological changes in the intact animal, latent changes following exposure of biological systems to ionizing radiations, factors influencing the biological response to ionizing radiation, relative effects of various ionizing radiations, and biological dosimetry.

  9. Improvement of Physico-Chemical Properties of Recycled (Elastomers /Thermoplastics) Composites using Ionizing Radiation

    International Nuclear Information System (INIS)

    Recycling of ground tire rubber (GRT) not only solves the waste disposal problem and maintains environmental quality, but also saves the valuable and limited resource of fossil feedstock. The major problem in the recycling of rubber-like materials such as tires is the cross linked molecular structure of already vulcanized rubber, which not only prevents the softening and processing of waste rubber particles but also inhibits binding of the powder surface to the virgin material. Several reclamation methods have proposed to overcome these barriers, which have basically followed two main approaches: (1) the de vulcanization of cured rubber and (2) the surface modifications of waste particles. The de vulcanization of rubber causes the cleavage of crosslinks via chemical treatments, which make used rubber suitable to be reformulated and recurred into new articles. In consequence, this work is mainly aimed to prepare of de vulcanized rubber (DR) and evaluating mechanical, thermal, and morphological properties of the thermoplastic vulcanizations (TPVs) based on de vulcanized rubber blended with polypropylene, EPDM using peroxide under the effect of radiation dose and DR feed ratio. The efficiency of the compounding process has been examined by infrared spectroscopy (FTIR), X-ray diffraction and scanning electron microscopy (SEM). The mechanical and thermal behaviors of the blends composed of de vulcanized rubber (DR) , high crystalline polypropylene (PP) and EPDM in different proportions were studied. Evaluation of the mechanical and thermal properties of the developed blends, unirradiated and gamma irradiated, was carried out using tensile strength (Ts), elongation at break (Eb), hardness, TGA and DSC measurements.

  10. [Determination of 16 polychlorinated biphenyls in fish oil by gas chromatography-negative ion chemical ionization-mass spectrometry].

    Science.gov (United States)

    Wang, Li; Li, Shushu; Zhang, Zhan; Wang, Shoulin; Li, Lei

    2015-08-01

    An analytical method for the simultaneous determination of 16 polychlorinated biphenyls (PCBs) in fish oil was developed. PCBs were extracted from fish oil with n-hexane, purified by sulfuric acid and determined by using gas chromatography-negative ion chemical ionization-mass spectrometry (GC-NCI-MS) in selected ion-monitoring (SIM) mode. A good linear relationship (r > 0.99) was observed with the PCBs concentrations from 0.01 µg/L to 10 µg/L, and the limits of quantification (LOQ, S/N = 10) were between 3 pg/g and 67 pg/g for different kinds of PCBs. The average recoveries ranged from 62.3% to 121.8% with the relative standard deviations ( RSDs, n = 3) smaller than 12%. Compared with the traditional pre-treatment of multiple material solid phase extraction, this new method is simple, rapid and less organic solvent usage. Meanwhile the method has good selectivity and sensitivity, and it is suitable for the determination of multiple trace PCBs in fish oil. PMID:26749866

  11. Simultaneous enantioselective determination of amphetamine and congeners in hair specimens by negative chemical ionization gas chromatography-mass spectrometry.

    Science.gov (United States)

    Martins, Liliane; Yegles, Michel; Chung, Heesun; Wennig, Robert

    2005-10-15

    Enantioselective quantification of amphetamine (AM), methamphetamine (MA), 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA) and 3,4-methylenedioxyethylamphetamine (MDEA) enantiomers in hair using gas chromatography-mass spectrometry (GC-MS) is described. Hair specimens were digested with 1M sodium hydroxide at 100 degrees C for 30 min and extracted by a solid phase procedure using Cleanscreen ZSDAU020. Extracted analytes were derivatised with (S)-heptafluorobutyrylprolyl chloride and the resulting diastereoisomers were quantified by GC-MS operating in the negative chemical ionization mode. Extraction yields were between 73.0 and 97.9%. Limits of detection varied in the range of 2.1-45.9 pg/mg hair, whereas the lowest limits of quantification varied between 4.3 and 91.8 pg/mg hair. Intra- and inter-assay precision and respective accuracy were acceptable. The enantiomeric ratios (R versus S) of AM, MA, MDA, MDMA and MDEA were determined in hair from suspected amphetamine abusers. Only MA and AM enantiomers were detectable in this collective and the quantification data showed in most cases higher concentrations of (R)-MA and (R)-AM than those of the corresponding (S)-enantiomers. PMID:16154523

  12. An improved reagent for determination of aliphatic amines with fluorescence and online atmospheric chemical ionization-mass spectrometry identification

    International Nuclear Information System (INIS)

    An improved reagent named 2-[2-(dibenzocarbazole)-ethoxy] ethyl chloroformate (DBCEC-Cl) for the determination of aliphatic amines by high-performance liquid chromatography (HPLC) with fluorescence detection and post-column online atmospheric chemical ionization-mass spectrometry (APCI-MS) identification has been developed. DBCEC-Cl could easily and quickly label aliphatic amines. Derivatives were stable enough to be efficiently analyzed by HPLC and showed an intense protonated molecular ion corresponding m/z [M+H]+ under APCI-MS in positive-ion mode. The ratios for fluorescence responses were IDBCEC-amine/IBCEC-amine = 1.02-1.60; IDBCEC-amine/IBCEOC-amine = 1.30-2.57; and IDBCEC-amine/IFMOC-amine = 2.20-4.12 (here, I was relative fluorescence intensity). The ratios for MS responses were ICDBCEC-amine/ICBCEC-amine = 4.16-29.31 and ICDBCEC-amine/ICBCEOC-amine = 1.23-2.47 (Here, IC: APCI-MS ion current intensity). Detection limits calculated from 0.0244 pmol injection, at a signal-to-noise ratio of 3, were 0.3-3.0 fmol. The relative standard deviations for within-day determination (n = 6) were 0.045-0.081% for retention time and 0.86-1.03% for peak area for the tested aliphatic amines. The mean intra- and inter-assay precision for all amine levels were 0.9991.

  13. An aircraft-borne chemical ionization – ion trap mass spectrometer (CI-ITMS for fast PAN and PPN measurements

    Directory of Open Access Journals (Sweden)

    H. Schlager

    2011-02-01

    Full Text Available An airborne chemical ionization ion trap mass spectrometer instrument (CI-ITMS has been developed for tropospheric and stratospheric fast in-situ measurements of PAN (peroxyacetyl nitrate and PPN (peroxypropionyl nitrate. The first scientific deployment of the FASTPEX instrument (FASTPEX = Fast Measurement of Peroxyacyl nitrates took place in the Arctic during 18 missions aboard the DLR research aircraft Falcon, within the framework of the POLARCAT-GRACE campaign in the summer of 2008. The FASTPEX instrument is described and characteristic properties of the employed ion trap mass spectrometer are discussed. Atmospheric data obtained at altitudes of up to ~12 km are presented, from the boundary layer to the lowermost stratosphere. Data were sampled with a time resolution of 2 s and a 2σ detection limit of 25 pmol mol−1. An isotopically labelled standard was used for a permanent on-line calibration. For this reason the accuracy of the PAN measurements is better than ±10% for mixing ratios greater than 200 pmol mol−1. PAN mixing ratios in the summer Arctic troposphere were in the order of a few hundred pmol mol−1 and generally correlated well with CO. In the Arctic boundary layer and lowermost stratosphere smaller PAN mixing ratios were observed due to a combination of missing local sources of PAN precursor gases and efficient removal processes (thermolysis/photolysis. PPN, the second most abundant PAN homologue, was measured simultaneously. Observed PPN/PAN ratios range between ~0.03 and 0.3.

  14. Determination of polybrominated biphenyls in Tasmanian devils (Sarcophilus harrisii) by gas chromatography coupled to electron capture negative ion tandem mass spectrometry or electron ionization high-resolution mass spectrometry.

    Science.gov (United States)

    Vetter, Walter; Recke, Roland von der; Symons, Robert; Pyecroft, Stephen

    2008-12-01

    Two gas chromatography/mass spectrometry (GC/MS) methods for the determination of polybrominated biphenyls (PBBs) by isotope dilution analysis (IDA) using (13)C(12)-PBB 153 in the presence of polybrominated diphenyl ethers (PBDEs) were compared. Recovery of (13)C(12)-PBB 153 which was added to the extracted lipids before sample purification was commenced ranged from 88-117% (mean value 98.2 +/- 8.9%). Nevertheless, IDA analysis of PBBs using (13)C(12)-labelled congeners is limited by the potential co-elution of PBBs with polybrominated diphenyl ethers (PBDEs). The pair PBB 153 and BDE 154 was inspected since M(+) and [M-2Br](+) ions of (13)C(12)-PBB 153 and BDE 154 were only separated by 4 u. Gas chromatography/electron ionization high-resolution mass spectrometry with selected ion monitoring (GC/EI-HRMS-SIM) was suitable when m/z 475.7449 and m/z 477.7429 were used for (13)C(12)-PBB 153 because they are below the monoisotopic peak of the [M-2Br](+) fragment ion of hexaBDEs at m/z 479.7. Gas chromatography/electron capture negative ion tandem mass spectrometry selected reaction monitoring (GC/ECNI-MS/MS-SRM) measurements could be applied because (13)C(12)-PBB 153 and BDE 154 were separated by GC on a 25-m Factor Four CP-Sil 8MS column.Comparative measurements with GC/EI-HRMS-SIM and GC/ECNI-MSMS-SRM were carried out with samples of Tasmanian devils from Tasmania (Australia), an endangered species due to a virus epidemy which has already proved fatal for half of the population. Both techniques verified concentrations of PBB 153 in the range 0.3-11 ng/g lipids with excellent agreement of the levels in all but two samples. The PBB residue pattern demonstrated that PBB pollution originated from the previous discharge with technical hexabromobiphenyl which is dominated by PBB 153. Other congeners such as PBB 132 and PBB 138 were detected in the Tasmanian devils but the proportions relative to PBB 153 were lower than in the technical product. Samples of healthy and

  15. Measurements of tropospheric HO2 and RO2 by oxygen dilution modulation and chemical ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    J. S. Olson

    2011-04-01

    Full Text Available An improved method for the measurement of hydroperoxy radicals (HO2 and organic peroxy radicals (RO2, where R is any organic group has been developed that combines two previous chemical conversion/chemical ionization mass spectrometry (CIMS peroxy radical measurement techniques. Applicable to both ground-based and aircraft platforms, the method provides good separation between HO2 and RO2, and frequent measurement capability with observations of both HO2 and HO2 + RO2 amounts each minute. These improvements allow for analyses of measured [HO2]/[HO2 + RO2] ratios on timescales relevant to tropospheric photochemistry. By varying both [NO] and [O2] simultaneously in the chemical conversion region of the PeRCIMS (Peroxy Radical CIMS inlet, the method exploits the changing conversion efficiency of RO2 to HO2 under different inlet [NO]/[O2] to selectively observe either primarily HO2 or the sum of HO2 and RO2. Two modes of operation have been established for ambient measurements: in the first half of the minute, RO2 radicals are measured at close to 100% efficiency along with HO2 radicals (low [NO]/[O2] = 2.53 × 10−5 and in the second half of the minute, HO2 is detected while the majority of ambient RO2 radicals are measured with low efficiency, approximately 15% (high [NO]/[O2] = 6.80 × 10−4. The method has been tested extensively in the laboratory under various conditions and for a variety of organic peroxy radicals relevant to the atmosphere and the results of these tests are presented. The modified PeRCIMS instrument has been deployed successfully using the new measurement technique on a number of aircraft campaigns, including on the NSF/NCAR C-130 during the MIRAGE-Mex and NASA INTEX-B field campaigns in the spring of 2006. A brief comparison of the peroxy radical measurements during these campaigns to a photochemical box model indicates good agreement under tropospheric conditions where NOx (NO + NO2 concentrations are lower than 0.5 ppb

  16. Measurements of tropospheric HO2 and RO2 by oxygen dilution modulation and chemical ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    J. S. Olson

    2010-09-01

    Full Text Available An improved method for the measurement of hydroperoxy radicals (HO2 and organic peroxy radicals (RO2, where R is any organic group has been developed that combines two previous chemical conversion/chemical ionization mass spectrometry (CIMS peroxy radical measurement techniques. Applicable to both ground-based and aircraft platforms, the method provides good separation between HO2 and RO2 and frequent measurement capability with observations of both HO2 and HO2 + RO2 amounts each minute. This allows for analyses of measured [HO2]/[HO2 + RO2] ratios on timescales relevant to tropospheric photochemistry. By varying both [NO] and [O2] simultaneously in the chemical conversion region of the PeRCIMS (Peroxy Radical CIMS inlet, the method exploits the changing conversion efficiency of RO2 to HO2 under different inlet [NO]/[O2] to selectively observe either primarily HO2 or the sum of HO2 and RO2. Two modes of operation have been established for ambient measurements: in the first half of the minute, RO2 radicals are measured at close to 100% efficiency along with HO2 radicals (low [NO]/[O2] = 2.53 × 10−5 and in the second half of the minute, HO2 is detected while the majority of ambient RO2 radicals are measured with approximately 15% efficiency (high [NO]/[O2] = 6.80 × 10−4. The method has been tested extensively in the laboratory under various conditions and for a variety of organic peroxy radicals relevant to the atmosphere and the results of these tests are presented. The modified PeRCIMS instrument has been deployed successfully using the current measurement technique on a number of aircraft campaigns, including on the NSF/NCAR C-130 during the MIRAGE-Mex and NASA INTEX-B field campaigns in the spring of 2006. A brief comparison of the peroxy radical measurements during these campaigns to a photochemical box model confirms that the PeRCIMS is able to successfully separate and measure HO2 and RO2 under the majority of tropospheric conditions.

  17. Measurements of tropospheric HO2 and RO2 by oxygen dilution modulation and chemical ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    J. S. Olson

    2011-01-01

    Full Text Available An improved method for the measurement of hydroperoxy radicals (HO2 and organic peroxy radicals (RO2, where R is any organic group has been developed that combines two previous chemical conversion/chemical ionization mass spectrometry (CIMS peroxy radical measurement techniques. Applicable to both ground-based and aircraft platforms, the method provides good separation between HO2 and RO2 and frequent measurement capability with observations of both HO2 and HO2+RO2 amounts each minute. This allows for analyses of measured [HO2]/[HO2+RO2] ratios on timescales relevant to tropospheric photochemistry. By varying both [NO] and [O2] simultaneously in the chemical conversion region of the PeRCIMS (Peroxy Radical CIMS inlet, the method exploits the changing conversion efficiency of RO2 to HO2 under different inlet [NO]/[O2] to selectively observe either primarily HO2 or the sum of HO2 and RO2. Two modes of operation have been established for ambient measurements: in the first half of the minute, RO2 radicals are measured at close to 100% efficiency along with HO2 radicals (low [NO]/[O2] = 2.53×10−5 and in the second half of the minute, HO2 is detected while the majority of ambient RO2 radicals are measured with low efficiency, approximately 15% (high [NO]/[O2] = 6.80×10−4. The method has been tested extensively in the laboratory under various conditions and for a variety of organic peroxy radicals relevant to the atmosphere and the results of these tests are presented. The modified PeRCIMS instrument has been deployed successfully using the new measurement technique on a number of aircraft campaigns, including on the NSF/NCAR C-130 during the MIRAGE-Mex and NASA INTEX-B field campaigns in the spring of 2006. A brief comparison of the peroxy radical measurements during these campaigns to a photochemical box model indicates good agreement under tropospheric conditions where NOx (NO+NO2 concentrations are lower than 0.5 ppbV (parts per billion by

  18. A novel method of liquid chromatography–tandem mass spectrometry combined with chemical derivatization for the determination of ribonucleosides in urine

    Energy Technology Data Exchange (ETDEWEB)

    Li, Shangfu [State Key Laboratory of Environmental and Biological Analysis, Department of Chemistry, Hong Kong Baptist University, Hong Kong (China); Jin, Yibao [Shenzhen Institute for Drug Control, Shenzhen 518055 (China); State Key Laboratory Breeding Base-Shenzhen Key Laboratory of Chemical Biology, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Tang, Zhi; Lin, Shuhai [State Key Laboratory of Environmental and Biological Analysis, Department of Chemistry, Hong Kong Baptist University, Hong Kong (China); Liu, Hongxia [State Key Laboratory Breeding Base-Shenzhen Key Laboratory of Chemical Biology, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Key Laboratory of Metabolomics at Shenzhen, Shenzhen 518055 (China); Jiang, Yuyang [State Key Laboratory Breeding Base-Shenzhen Key Laboratory of Chemical Biology, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Cai, Zongwei, E-mail: zwcai@hkbu.edu.hk [State Key Laboratory of Environmental and Biological Analysis, Department of Chemistry, Hong Kong Baptist University, Hong Kong (China)

    2015-03-15

    Highlights: • A simple, robust and low-cost derivatization method was reported for ribonucleoside determination for the first time. • Improvement of separation and enhancement of sensitivity were achieved by using the derivatization approach. • Isotope labeling method with acetone-d{sub 6} and multivariate statistical analysis facilitated ribonucleoside identification. • Application of the method enabled the positive identification of 56 ribonucleosides. - Abstract: Ribonucleosides are the end products of RNA metabolism. These metabolites, especially the modified ribonucleosides, have been extensively evaluated as cancer-related biomarkers. However, the determination of urinary ribonucleosides is still a challenge due to their low abundance, high polarity and serious matrix interferences in urine samples. In this study, a derivatization method based on a chemical reaction between ribonucleosides and acetone to form acetonides was developed for the determination of urinary ribonucleosides. The derivative products, acetonides, were detected by using liquid chromatography–tandem mass spectrometry (LC–MS/MS). The methodological evaluation was performed by quantifying four nucleosides for linear range, average recovery, precision, accuracy and stability. The validated procedures were applied to screen modified ribonucleosides in urine samples. Improvement of separation and enhancement of sensitivity were obtained in the analysis. To identify ribonucleosides, inexpensive isotope labeling acetone (acetone-d{sub 6}) and label-free acetone were applied to form ordinary and deuterated acetonides, respectively. The two groups of samples were separated with orthogonal partial least squares (OPLS). The ordinary and deuterated pairs of acetonides were symmetrically distributed in the S-plot for easy and visual signal identification. After structural confirmation, a total of 56 ribonucleosides were detected, 52 of which were modified ribonucleosides. The application

  19. A novel method of liquid chromatography–tandem mass spectrometry combined with chemical derivatization for the determination of ribonucleosides in urine

    International Nuclear Information System (INIS)

    Highlights: • A simple, robust and low-cost derivatization method was reported for ribonucleoside determination for the first time. • Improvement of separation and enhancement of sensitivity were achieved by using the derivatization approach. • Isotope labeling method with acetone-d6 and multivariate statistical analysis facilitated ribonucleoside identification. • Application of the method enabled the positive identification of 56 ribonucleosides. - Abstract: Ribonucleosides are the end products of RNA metabolism. These metabolites, especially the modified ribonucleosides, have been extensively evaluated as cancer-related biomarkers. However, the determination of urinary ribonucleosides is still a challenge due to their low abundance, high polarity and serious matrix interferences in urine samples. In this study, a derivatization method based on a chemical reaction between ribonucleosides and acetone to form acetonides was developed for the determination of urinary ribonucleosides. The derivative products, acetonides, were detected by using liquid chromatography–tandem mass spectrometry (LC–MS/MS). The methodological evaluation was performed by quantifying four nucleosides for linear range, average recovery, precision, accuracy and stability. The validated procedures were applied to screen modified ribonucleosides in urine samples. Improvement of separation and enhancement of sensitivity were obtained in the analysis. To identify ribonucleosides, inexpensive isotope labeling acetone (acetone-d6) and label-free acetone were applied to form ordinary and deuterated acetonides, respectively. The two groups of samples were separated with orthogonal partial least squares (OPLS). The ordinary and deuterated pairs of acetonides were symmetrically distributed in the S-plot for easy and visual signal identification. After structural confirmation, a total of 56 ribonucleosides were detected, 52 of which were modified ribonucleosides. The application of

  20. 直接进样电喷雾串联质谱法测定草鱼肌肉组织中磷脂%Determination of Phospholipids from Ctenopharyngodon Idellus Muscle by Direct-injection Electrospray Ionization Tandem Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    王友谊; 张虹; 戴志远

    2012-01-01

    A method was developed for the determination of phospholipids from Ctenopharyngodon idellus muscle by direct-injection electrospray ionization tandem mass spectrometry (ESI-MS/MS). The samples were extracted with modified Bligh Dyer method and the crude extracts were taken directly into the electrospray ionization source by syringe pump. Under the precursor ion scan and neutral loss scan) intrasource separation and identification of six classes of phospholipids including phosphatidyl choline, phosphatidyl ethanolamine, phosphatidyl inositoU phosphatidyl serine, phos-phatidyl glycerol and phosphatidic acid were achieved. The intensity of quasi-molecular ion of the phospholipids and concentration showed good linear relation in a certain range. The recoveries (67.1% -96.6%) and precision meet the requirements for analyzing biological samples. This method has been applied to analyze the molecular species and content of four class phospholipids from Cteno-pharyngodon idellus muscle. The method is simple, fast accurate, and reproducibility with excellent stability, and suitable to analyze phospholipids from various biological samples for lipidomics research.%建立了直接进样电喷雾串联质谱测定草鱼肌肉组织中磷脂的方法.以Bligh Dyer法提取总脂质,采用流动注射泵直接进样的方式将样品导人电喷雾离子源,利用串联三重四级杆质谱的母离子扫描和中性丢失扫描功能,通过扫描磷脂的特征性子离子或中性质量丢失实现对磷脂酰胆碱、磷脂酰乙醇胺、磷脂酰肌醇、磷脂酰丝氨酸、磷脂酰甘油和磷脂酸六类磷脂的源内分离和鉴定.结果显示,在-定的浓度范围内,磷脂的浓度与磷脂直接进样电喷雾电离后形成准分子离子的响应值呈现良好的线性关系,回收率(67.1%~96.6%)和精密度可以满足生物样品分析的要求.采用本方法测定了草鱼肌肉组织中磷脂酰胆碱、磷脂酰乙醇胺、磷脂

  1. Gaseous and particulate composition of fresh and aged emissions of diesel, RME and CNG buses using Chemical Ionization Mass Spectrometry

    Science.gov (United States)

    Psichoudaki, Magda; Le Breton, Michael; Hallquist, Mattias; Watne, Ågot; Hallquist, Asa

    2016-04-01

    . A Time-of-Flight Chemical Ionization Mass Spectrometer (ToF-CIMS) was employed to monitor the concentration of different organic species present in the fresh and aged emissions. This instrument is capable of identifying the molecular formulas of species in the gas phase. The FIGAERO inlet, also enabled the characterisation of the particle phase, as particles were simultaneously collected on a filter, from which they could then be thermally desorbed and detected. Acetate (negative) ionization was utilised to allow high sensitivity measurements of organic acids, aldehydes, ketones, diols and halogenated species. The H2O, O3 and NOx concentrations inside the PAM flow reactor were monitored, and an organic tracer for OH exposure was also continuously measured. The concentrations of dominant species in both fresh and aged gaseous and particulate bus emissions from the different fuel types will be presented as well as their emission factors, calculated from concurrent CO2 measurements.

  2. The effect of H2SO4 – amine clustering on chemical ionization mass spectrometry (CIMS) measurements of gas-phase sulfuric acid

    OpenAIRE

    Kurtén, T.; T. Petäjä; Smith,J; Ortega, I.K.; Sipilä, M.; Junninen, H.; M. Ehn; Vehkamäki, H.; Mauldin, L.; Worsnop, D.R.; M. Kulmala

    2011-01-01

    The state-of-the art method for measuring atmospheric gas-phase sulfuric acid is chemical ionization mass spectrometry (CIMS) based on nitrate reagent ions. We have assessed the possible effect of the sulfuric acid molecules clustering with base molecules on CIMS measurements using computational chemistry. From the computational data, three conclusions can be drawn. First, a significant fraction of the gas-phase sulfuric acid molecules are very likely clustered with amines i...

  3. Influence of radiation on some physico-chemical properties of gum acacia. Mitigation of degradation by different class of antioxidants in LDPE expose to ionizing radiations

    International Nuclear Information System (INIS)

    Controlling of degradation in polysaccharide is also gaining impetus from commercial point of view. Comprehensive studies on the influence of ionizing radiation on the physico-chemical properties of polysaccharides are very important for their applications in different industries. The effect of gamma radiation on gum acacia has been studied and its effect on some physico-chemical properties, as measured by UV spectroscopy and viscometry has been discussed. The gum samples are irradiated in the range of 5 kGy to 25 kGy both in air and vacuum. Samples irradiated under vacuum shows colour stability while viscosity remain unaffected. (author)

  4. Dosimetry of ionizing radiation

    International Nuclear Information System (INIS)

    The publication deals with a major field of ionizing radiation dosimetry, viz., integrating dosimetric methods, which are the basic means of operative dose determination. It is divided into the following sections: physical and chemical effects of ionizing radiation; integrating dosimetric methods for low radiation doses (film dosimetry, nuclear emulsions, thermoluminescence, radiophotoluminescence, solid-state track detectors, integrating ionization dosemeters); dosimetry of high ionizing radiation doses (chemical dosimetric methods, dosemeters based on the coloring effect, activation detectors); additional methods applicable to integrating dosimetry (exoelectron emission, electron spin resonance, lyoluminescence, etc.); and calibration techniques for dosimetric instrumentation. (Z.S.). 422 refs

  5. Evaluation of Offline Tandem and Online Solid-Phase Extraction with Liquid Chromatography/Electrospray Ionization-Mass Spectrometry for Analysis of Antibiotics in Ambient Water and Comparison to an Independent Method

    Science.gov (United States)

    Meyer, M.T.; Lee, E.A.; Ferrell, G.M.; Bumgarner, J.E.; Varns, Jerry

    2007-01-01

    This report describes the performance of an offline tandem solid-phase extraction (SPE) method and an online SPE method that use liquid chromatography/mass spectrometry for the analysis of 23 and 35 antibiotics, respectively, as used in several water-quality surveys conducted since 1999. In the offline tandem SPE method, normalized concentrations for the quinolone, macrolide, and sulfonamide antibiotics in spiked environmental samples averaged from 81 to 139 percent of the expected spiked concentrations. A modified standard-addition technique was developed to improve the quantitation of the tetracycline antibiotics, which had 'apparent' concentrations that ranged from 185 to 1,200 percent of their expected spiked concentrations in matrix-spiked samples. In the online SPE method, normalized concentrations for the quinolone, macrolide, sulfonamide, and tetracycline antibiotics in matrix-spiked samples averaged from 51 to 142 percent of their expected spiked concentrations, and the beta-lactam antibiotics in matrix-spiked samples averaged from 22 to 76 percent of their expected spiked concentration. Comparison of 44 samples analyzed by both the offline tandem SPE and online SPE methods showed 50 to 100 percent agreement in sample detection for overlapping analytes and 68 to 100 percent agreement in a presence-absence comparison for all analytes. The offline tandem and online SPE methods were compared to an independent method that contains two overlapping antibiotic compounds, sulfamethoxazole and trimethoprim, for 96 and 44 environmental samples, respectively. The offline tandem SPE showed 86 and 92 percent agreement in sample detection and 96 and 98 percent agreement in a presence-absence comparison for sulfamethoxazole and trimethoprim, respectively. The online SPE method showed 57 and 56 percent agreement in sample detection and 72 and 91 percent agreement in presence-absence comparison for sulfamethoxazole and trimethoprim, respectively. A linear regression with

  6. Online measurement of biogenic organic acids in the boreal forest using atmospheric pressure chemical ionization mass spectrometry (APCI-MS)

    Science.gov (United States)

    Vogel, A. L.; Brüggemann, M.; ńijälä, M.; Ehn, M.; Junninen, H.; Corrigan, A. L.; Petäjä, T.; Worsnop, D. R.; Russell, L. M.; Kulmala, M.; Williams, J.; Hoffmann, T.

    2012-04-01

    Emission of biogenic volatile organic compounds (BVOCs) by vegetation in the boreal forest and their subsequent atmospheric oxidation leads to the formation of secondary organic aerosol (SOA) which has important impacts on climate and human health. Oxidation of BVOCs produces a variety of mostly unidentified species in oxygenated organic aerosol (OOA). Presently aerosol mass spectrometers (AMS) are able to determine quantitative information about the relative oxygen to carbon content of organic aerosols and thereby reveal the photochemical age and volatility of organic aerosol by distinguishing between low volatile oxygenated organic aerosol (LV-OOA), semivolatile oxygenated organic aerosol (SV-OOA) and hydrocarbon like organic aerosol (HOA)[1]. However, the AMS can usually not be used to measure and quantify single organic compounds such as individual biogenic organic marker compounds. Here we show the results of online measurements of gas and particle phase biogenic acids during HUMPPA-COPEC 2010 at Hyytiälä, Finland. This was achieved by coupling a self built miniature Versatile Aerosol Concentration Enrichment System (mVACES) as described by Geller et al. [2] with an Atmospheric Pressure Chemical Ionization Ion Trap Mass Spectrometer (APCI IT MS; Hoffmann et al., [3]). The benefits of the on-line APCI-MS are soft ionization with little fragmentation compared to AMS, high measurement frequency and less sampling artifacts than in the common procedure of taking filter samples, extraction and detection with LC-MS. Furthermore, the ion trap of the instrument allows MS/MS experiments to be performed by isolation of single m/z ratios of selected molecular species. By subsequent addition of energy, the trapped ions form characteristic fragments which enable structural insight on the molecular level. Comparison of APCI-MS data to AMS data, acquired with a C-ToF-AMS [4], revealed a good correlation coefficient for total organics and sulphate. Furthermore, data show

  7. Are clusters important in understanding the mechanisms in atmospheric pressure ionization? Part 1: Reagent ion generation and chemical control of ion populations.

    Science.gov (United States)

    Klee, Sonja; Derpmann, Valerie; Wißdorf, Walter; Klopotowski, Sebastian; Kersten, Hendrik; Brockmann, Klaus J; Benter, Thorsten; Albrecht, Sascha; Bruins, Andries P; Dousty, Faezeh; Kauppila, Tiina J; Kostiainen, Risto; O'Brien, Rob; Robb, Damon B; Syage, Jack A

    2014-08-01

    It is well documented since the early days of the development of atmospheric pressure ionization methods, which operate in the gas phase, that cluster ions are ubiquitous. This holds true for atmospheric pressure chemical ionization, as well as for more recent techniques, such as atmospheric pressure photoionization, direct analysis in real time, and many more. In fact, it is well established that cluster ions are the primary carriers of the net charge generated. Nevertheless, cluster ion chemistry has only been sporadically included in the numerous proposed ionization mechanisms leading to charged target analytes, which are often protonated molecules. This paper series, consisting of two parts, attempts to highlight the role of cluster ion chemistry with regard to the generation of analyte ions. In addition, the impact of the changing reaction matrix and the non-thermal collisions of ions en route from the atmospheric pressure ion source to the high vacuum analyzer region are discussed. This work addresses such issues as extent of protonation versus deuteration, the extent of analyte fragmentation, as well as highly variable ionization efficiencies, among others. In Part 1, the nature of the reagent ion generation is examined, as well as the extent of thermodynamic versus kinetic control of the resulting ion population entering the analyzer region. PMID:24850441

  8. Sensitive monitoring of monoterpene metabolites in human urine using two-step derivatisation and positive chemical ionisation-tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, Lukas [Institute and Outpatient Clinic of Occupational, Social and Environmental Medicine, University of Erlangen-Nuremberg, Schillerstrasse 25/29, 91054 Erlangen (Germany); Belov, Vladimir N. [Max Planck Institute for Biophysical Chemistry, Facility for Synthetic Chemistry, Am Fassberg 11, 37077 Göttingen (Germany); Göen, Thomas, E-mail: Thomas.Goeen@ipasum.med.uni-erlangen.de [Institute and Outpatient Clinic of Occupational, Social and Environmental Medicine, University of Erlangen-Nuremberg, Schillerstrasse 25/29, 91054 Erlangen (Germany)

    2013-09-02

    Highlights: •Sensitive monitoring of 10 metabolites of (R)-limonene, α-pinene, and Δ{sup 3}-carene in human urine samples. •Fast and simple sample preparation and derivatisation procedure using two-step silylation for unreactive tertiary hydroxyl groups. •Synthesis of reference substances and isotopically labelled internal standards of (R)-limonene, α-pinene, and Δ{sup 3}-carene metabolites. •Study on (R)-limonene, α-pinene, and Δ{sup 3}-carene metabolite background exposure of 36 occupationally unexposed volunteers. -- Abstract: A gas chromatographic–positive chemical ionisation-tandem mass spectrometric (GC–PCI-MS/MS) method for the simultaneous determination of 10 oxidative metabolites of the monoterpenoid hydrocarbons α-pinene, (R)-limonene, and Δ{sup 3}-carene ((+)-3-carene) in human urine was developed and tested for the monoterpene biomonitoring of the general population (n = 36). The method involves enzymatic cleavage of the glucuronides followed by solid-supported liquid–liquid extraction and derivatisation using a two-step reaction with N,O-bis(trimethylsilyl)-trifluoroacetamide and N-(trimethylsilyl)imidazole. The method proved to be both sensitive and reliable with detection limits ranging from 0.1 to 0.3 μg L{sup −1}. In contrast to the frequent and distinct quantities of (1S,2S,4R)-limonene-1,2-diol, the (1R,2R,4R)-stereoisomer could not be detected. The expected metabolite of (+)-3-carene, 3-caren-10-ol was not detected in any of the samples. All other metabolites were detected in almost all urine samples. The procedure enables for the first time the analysis of trace levels of a broad spectrum of mono- and bicyclic monoterpenoid metabolites (alcohols, diols, and carboxylic acids) in human urine. This analytical procedure is a powerful tool for population studies as well as for the discovery of human metabolism and toxicokinetics of monoterpenes.

  9. Computational and Experimental Assessment of Benzene Cation Chemistry for the Measurement of Marine Derived Biogenic Volatile Organic Compounds with Chemical Ionization Mass Spectrometry

    Science.gov (United States)

    Zoerb, M.; Kim, M.; Zimmermann, K.; Bertram, T. H.

    2013-12-01

    Chemical ionization mass spectrometry (CIMS) is a highly selective and sensitive technique for the measurement of trace gases in the atmosphere. However, competing side reactions and dependence on relative humidity (RH) can make the transition from the laboratory to the field challenging. Effective implementation of chemical ionization requires a thorough knowledge of the elementary steps leading to ionization of the analyte. We have recently investigated benzene cations for the detection of marine derived biogenic volatile organic compounds (BVOCs), such isoprene and terpene compounds, from algal bloom events. Our experimental results indicate that benzene ion chemistry is an attractive candidate for field measurements, and the RH dependence is weak. To further understand the advantages and limitations of this approach, we have also used electronic structure theory calculations to compliment the experimental work. These theoretical methods can provide valuable insight into the physical chemistry of ion molecule reactions including thermodynamical information, the stability of ions to fragmentation, and potential sources of interference such as dehydration to form isobaric ions. The combined experimental and computational approach also allows validation of the theoretical methods and will provide useful information towards gaining predictive power for the selection of appropriate reagent ions for future experiments.

  10. Gas Chromatography/Atmospheric Pressure Chemical Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry of Pyrolysis Oil from German Brown Coal.

    Science.gov (United States)

    Zuber, Jan; Kroll, Marius M; Rathsack, Philipp; Otto, Matthias

    2016-01-01

    Pyrolysis oil from the slow pyrolysis of German brown coal from Schöningen, obtained at a temperature of 500°C, was separated and analyzed using hyphenation of gas chromatography with an atmospheric pressure chemical ionization source operated in negative ion mode and Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS). Development of this ultrahigh-resolving analysis method is described, that is, optimization of specific GC and APCI parameters and performed data processing. The advantages of GC-APCI-FT-ICR-MS hyphenation, for example, soft ionization, ultrahigh-resolving detection, and most important isomer separation, were demonstrated for the sample liquid. For instance, it was possible to separate and identify nine different propylphenol, ethylmethylphenol, and trimethylphenol isomers. Furthermore, homologous series of different acids, for example, alkyl and alkylene carboxylic acids, were verified, as well as homologous series of alkyl phenols, alkyl dihydroxy benzenes, and alkoxy alkyl phenols. PMID:27066076

  11. A quantum chemical study from a molecular perspective: ionization and electron attachment energies for species often used to fabricate single-molecule junctions

    CERN Document Server

    Baldea, Ioan

    2015-01-01

    The accurate determination of the lowest electron attachment ($EA$) and ionization ($IP$) energies for molecules embedded in molecular junctions is important for correctly estimating, \\emph{e.g.}, the magnitude of the currents ($I$) or the biases ($V$) where an $I-V$-curve exhibits a significant non-Ohmic behavior. Benchmark calculations for the lowest electron attachment and ionization energies of several typical molecules utilized to fabricate single-molecule junctions characterized by n-type conduction (4,4'-bipyridine, 1,4-dicyanobenzene, and 4,4'-dicyano-1,1'-biphenyl) and p-type conduction (benzenedithiol, biphenyldithiol, hexanemonothiol, and hexanedithiol] based on the EOM-CCSD (equation-of-motion coupled-cluster singles and doubles) state-of-the-art method of quantum chemistry are presented. They indicate significant differences from the results obtained within current approaches to molecular transport. The present study emphasizes that, in addition to a reliable quantum chemical method, basis sets m...

  12. Quantum chemical calculations of ionization potentials and dimerization energies of ozone and chloro-oxides: two easy cases and a difficult one

    International Nuclear Information System (INIS)

    Ionization potentials (IPs) of Cl2O and of Clo2 and their dimers were recently measured via electron impact ionization close to threshold. For these systems, quantum chemical calculations were performed to verify the experimental results, to find the equilibrium structures of the three dimers and to obtain information about the electronic structure of monometers and dimers. It turns out that the two chloro-oxides pose no particular difficulties (Cl2O: 11.15 eV and ClO2: 10.55 eV; dimers ∼0.5 eV lower) but that in case of ozone measurement and calculation disagree severely. This lead to an investigation of the structure of ozone dimer and it is suggested that not a weekly bound O3+O3 complex but an O6 or O4+O2 entity is causing the signal. (nevyjel)

  13. Gas Chromatography/Atmospheric Pressure Chemical Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry of Pyrolysis Oil from German Brown Coal

    Directory of Open Access Journals (Sweden)

    Jan Zuber

    2016-01-01

    Full Text Available Pyrolysis oil from the slow pyrolysis of German brown coal from Schöningen, obtained at a temperature of 500°C, was separated and analyzed using hyphenation of gas chromatography with an atmospheric pressure chemical ionization source operated in negative ion mode and Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS. Development of this ultrahigh-resolving analysis method is described, that is, optimization of specific GC and APCI parameters and performed data processing. The advantages of GC-APCI-FT-ICR-MS hyphenation, for example, soft ionization, ultrahigh-resolving detection, and most important isomer separation, were demonstrated for the sample liquid. For instance, it was possible to separate and identify nine different propylphenol, ethylmethylphenol, and trimethylphenol isomers. Furthermore, homologous series of different acids, for example, alkyl and alkylene carboxylic acids, were verified, as well as homologous series of alkyl phenols, alkyl dihydroxy benzenes, and alkoxy alkyl phenols.

  14. Ionization structure and chemical abundances of the Wolf-Rayet nebula NGC 6888 with integral field spectroscopy

    Science.gov (United States)

    Fernández-Martín, A.; Martín-Gordón, D.; Vílchez, J. M.; Pérez Montero, E.; Riera, A.; Sánchez, S. F.

    2012-05-01

    Context. The study of nebulae around Wolf-Rayet (WR) stars gives us clues about the mass-loss history of massive stars, as well as about the chemical enrichment of the interstellar medium (ISM). Aims: This work aims to search for the observational footprints of the interactions between the ISM and stellar winds in the WR nebula NGC 6888 in order to understand its ionization structure, chemical composition, and kinematics. Methods: We have collected a set of integral field spectroscopy observations across NGC 6888, obtained with PPAK in the optical range performing both 2D and 1D analyses. Attending to the 2D analysis in the northeast part of NGC 6888, we have generated maps of the extinction structure and electron density. We produced statistical frequency distributions of the radial velocity and diagnostic diagrams. Furthermore, we performed a thorough study of integrated spectra in nine regions over the whole nebula. Results: The 2D study has revealed two main behaviours. We have found that the spectra of a localized region to the southwest of this pointing can be represented well by shock models assuming n = 1000 cm-3, twice solar abundances, and shock velocities from 250 to 400 km s-1. With the 1D analysis we derived electron densities ranging from <100 to 360 cm-3. The electron temperature varies from ~7700 K to ~10 200 K. A strong variation of up to a factor 10 between different regions in the nitrogen abundance has been found: N/H appears lower than the solar abundance in those positions observed at the edges and very enhanced in the observed inner parts. Oxygen appears slightly underabundant with respect to solar value, whereas the helium abundance is found to be above it. We propose a scenario for the evolution of NGC 6888 to explain the features observed. This scheme consists of a structure of multiple shells: i) an inner and broken shell with material from the interaction between the supergiant and WR shells, presenting an overabundance in N/H and a

  15. Simultaneous determination of hydroxycinnamates and catechins in human urine samples by column switching liquid chromatography coupled to atmospheric pressure chemical ionization mass spectrometry

    DEFF Research Database (Denmark)

    Nielsen, Salka E.; Sandström, B.

    2003-01-01

    atmospheric pressure chemical ionization (APCI) MS using single ion monitoring (SIM) in negative mode. Linear calibration graphs were achieved in the dynamic range of 10-1000 ng/ml urine. The inter- and intraassay coefficients of variation (C.V.%) for the analysis of the four compounds in quality control...... urine samples were between 7.8 and 10.9, n=17 (reproducibility), and the repeatability of the assay was between 2.5 and 5.0% (n = 12). Analyses of urine samples from a human dietary intervention study with intake of 600 g of fruits and vegetables were demonstrated. To our knowledge, this is the first...

  16. 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, S. E.; Freese, R.; Cornett, Claus;

    2000-01-01

    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 in...... variation for the analysis of the 12 different flavonoids in quality control urine samples were 12.3% on average (range 11.0-13.7%, n = 24, reproducibility) and the repeatability of the assay were 5.0% (mean, range 0.1-14.8%, it = 12). A subset of 10 urine samples from a human dietary intervention study...

  17. Irradiation dose assessment in persons exposed to ionizing radiation through extrapolation of data from clinic-chemical changes in irradiated laboratory animals

    International Nuclear Information System (INIS)

    An attempt is made to determine the dose within 24,48 and 72 hours of eventual exposure of healthy individuals to ionizing radiation through extrapolation of data retrieved from rats exposed to irradiation with 1, 3, 6 and 9 Gy X-rays. Seven clinic-chemical parameters are used: urea in the urine, taurine in the urine, urea in the serum, serum alkaline phosphatase, total serum lipids, sialic acid and thromboxane in the serum. A special formula is worked out and used for extrapolation of the experimental data, retrieved from irradiated rats, with due consideration to differences in the intensity of metabolic processes and species' radiosensitivity of rats and humans. The values of the aforementioned parameters that could be obtained upon eventual exposure of persons to ionizing irradiation are determined through computerization of the experimental data. It is believed that an accessible model for radiation dose assessment in the first three days after accidental exposure of human beings to ionizing irradiation is created. 5 refs., 4 figs. (author)

  18. Quantitative measurement of the chemical composition of geological standards with a miniature laser ablation/ionization mass spectrometer designed for in situ application in space research

    Science.gov (United States)

    Neuland, M. B.; Grimaudo, V.; Mezger, K.; Moreno-García, P.; Riedo, A.; Tulej, M.; Wurz, P.

    2016-03-01

    A key interest of planetary space missions is the quantitative determination of the chemical composition of the planetary surface material. The chemical composition of surface material (minerals, rocks, soils) yields fundamental information that can be used to answer key scientific questions about the formation and evolution of the planetary body in particular and the Solar System in general. We present a miniature time-of-flight type laser ablation/ionization mass spectrometer (LMS) and demonstrate its capability in measuring the elemental and mineralogical composition of planetary surface samples quantitatively by using a femtosecond laser for ablation/ionization. The small size and weight of the LMS make it a remarkable tool for in situ chemical composition measurements in space research, convenient for operation on a lander or rover exploring a planetary surface. In the laboratory, we measured the chemical composition of four geological standard reference samples USGS AGV-2 Andesite, USGS SCo-l Cody Shale, NIST 97b Flint Clay and USGS QLO-1 Quartz Latite with LMS. These standard samples are used to determine the sensitivity factors of the instrument. One important result is that all sensitivity factors are close to 1. Additionally, it is observed that the sensitivity factor of an element depends on its electron configuration, hence on the electron work function and the elemental group in agreement with existing theory. Furthermore, the conformity of the sensitivity factors is supported by mineralogical analyses of the USGS SCo-l and the NIST 97b samples. With the four different reference samples, the consistency of the calibration factors can be demonstrated, which constitutes the fundamental basis for a standard-less measurement-technique for in situ quantitative chemical composition measurements on planetary surface.

  19. Quantitative measurement of the chemical composition of geological standards with a miniature laser ablation/ionization mass spectrometer designed for in situ application in space research

    International Nuclear Information System (INIS)

    A key interest of planetary space missions is the quantitative determination of the chemical composition of the planetary surface material. The chemical composition of surface material (minerals, rocks, soils) yields fundamental information that can be used to answer key scientific questions about the formation and evolution of the planetary body in particular and the Solar System in general. We present a miniature time-of-flight type laser ablation/ionization mass spectrometer (LMS) and demonstrate its capability in measuring the elemental and mineralogical composition of planetary surface samples quantitatively by using a femtosecond laser for ablation/ionization. The small size and weight of the LMS make it a remarkable tool for in situ chemical composition measurements in space research, convenient for operation on a lander or rover exploring a planetary surface. In the laboratory, we measured the chemical composition of four geological standard reference samples USGS AGV-2 Andesite, USGS SCo-l Cody Shale, NIST 97b Flint Clay and USGS QLO-1 Quartz Latite with LMS. These standard samples are used to determine the sensitivity factors of the instrument. One important result is that all sensitivity factors are close to 1. Additionally, it is observed that the sensitivity factor of an element depends on its electron configuration, hence on the electron work function and the elemental group in agreement with existing theory. Furthermore, the conformity of the sensitivity factors is supported by mineralogical analyses of the USGS SCo-l and the NIST 97b samples. With the four different reference samples, the consistency of the calibration factors can be demonstrated, which constitutes the fundamental basis for a standard-less measurement-technique for in situ quantitative chemical composition measurements on planetary surface. (paper)

  20. Use of a hand-portable gas chromatograph-toroidal ion trap mass spectrometer for self-chemical ionization identification of degradation products related to O-ethyl S-(2-diisopropylaminoethyl) methyl phosphonothiolate (VX)

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Philip A., E-mail: Smith.Philip.A@dol.gov [Uniformed Services University of the Health Sciences, Department of Preventive Medicine and Biometrics, 4301 Jones Bridge Road, Bethesda, MD, 20814 (United States); Lepage, Carmela R. Jackson [Defence R and D Canada - Suffield, Box 400, Station Main, Medicine Hat, Alberta, T1A 8K6 (Canada); Savage, Paul B. [Brigham Young University, Department of Chemistry and Biochemistry, Provo, UT, 84602 (United States); Bowerbank, Christopher R.; Lee, Edgar D. [Torion Technologies Inc., 796 East Utah Valley Drive, Suite 200, American Fork, UT, 84003 (United States); Lukacs, Michael J. [Defence R and D Canada - Suffield, Box 400, Station Main, Medicine Hat, Alberta, T1A 8K6 (Canada)

    2011-04-01

    The chemical warfare agent O-ethyl S-(2-diisopropylaminoethyl) methyl phosphonothiolate (VX) and many related degradation products produce poorly diagnostic electron ionization (EI) mass spectra by transmission quadrupole mass spectrometry. Thus, chemical ionization (CI) is often used for these analytes. In this work, pseudomolecular ([M+H]{sup +}) ion formation from self-chemical ionization (self-CI) was examined for four VX degradation products containing the diisopropylamine functional group. A person-portable toroidal ion trap mass spectrometer with a gas chromatographic inlet was used with EI, and both fixed-duration and feedback-controlled ionization time. With feedback-controlled ionization, ion cooling (reaction) times and ion formation target values were varied. Evidence for protonation of analytes was observed under all conditions, except for the largest analyte, bis(diisopropylaminoethyl)disulfide which yielded [M+H]{sup +} ions only with increased fixed ionization or ion cooling times. Analysis of triethylamine-d{sub 15} provided evidence that [M+H]{sup +} production was likely due to self-CI. Analysis of a degraded VX sample where lengthened ion storage and feedback-controlled ionization time were used resulted in detection of [M+H]{sup +} ions for VX and several relevant degradation products. Dimer ions were also observed for two phosphonate compounds detected in this sample.

  1. An isotope-labeled chemical derivatization method for the quantitation of short-chain fatty acids in human feces by liquid chromatography–tandem mass spectrometry

    International Nuclear Information System (INIS)

    Highlights: • 3-Nitrophenylhydrazine was used to derivatize short-chain fatty acids (SCFAs) for LC-MS/MS. • 13C6 analogues were produced for use as isotope-labeled internal standards. • Isotope-labeled standards compensate for ESI matrix effects in LC-MS/MS. • Femtomolar sensitivities and 93–108% quantitation accuracy were achieved for human fecal SCFAs. - Abstract: Short-chain fatty acids (SCFAs) are produced by anaerobic gut microbiota in the large bowel. Qualitative and quantitative measurements of SCFAs in the intestinal tract and the fecal samples are important to understand the complex interplay between diet, gut microbiota and host metabolism homeostasis. To develop a new LC-MS/MS method for sensitive and reliable analysis of SCFAs in human fecal samples, 3-nitrophenylhydrazine (3NPH) was employed for pre-analytical derivatization to convert ten C2–C6 SCFAs to their 3-nitrophenylhydrazones under a single set of optimized reaction conditions and without the need of reaction quenching. The derivatives showed excellent in-solution chemical stability. They were separated on a reversed-phase C18 column and quantitated by negative-ion electrospray ionization – multiple-reaction monitoring (MRM)/MS. To achieve accurate quantitation, the stable isotope-labeled versions of the derivatives were synthesized in a single reaction vessel from 13C6-3NPH, and were used as internal standard to compensate for the matrix effects in ESI. Method validation showed on-column limits of detection and quantitation over the range from low to high femtomoles for the ten SCFAs, and the intra-day and inter-day precision for determination of nine of the ten SCFAs in human fecal samples was ≤8.8% (n = 6). The quantitation accuracy ranged from 93.1% to 108.4% (CVs ≤ 4.6%, n = 6). This method was used to determine the SCFA concentrations and compositions in six human fecal samples. One of the six samples, which was collected from a clinically diagnosed type 2 diabetes

  2. An isotope-labeled chemical derivatization method for the quantitation of short-chain fatty acids in human feces by liquid chromatography–tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Han, Jun; Lin, Karen; Sequeira, Carita [University of Victoria – Genome BC Proteomics Centre, University of Victoria, Vancouver Island Technology Park, 3101–4464 Markham Street, Victoria, BC V8Z 7X8 (Canada); Borchers, Christoph H., E-mail: christoph@proteincentre.com [University of Victoria – Genome BC Proteomics Centre, University of Victoria, Vancouver Island Technology Park, 3101–4464 Markham Street, Victoria, BC V8Z 7X8 (Canada); Department of Biochemistry and Microbiology, University of Victoria, Petch Building Room 207, 3800 Finnerty Road, Victoria, BC V8P 5C2 (Canada)

    2015-01-07

    Highlights: • 3-Nitrophenylhydrazine was used to derivatize short-chain fatty acids (SCFAs) for LC-MS/MS. • {sup 13}C{sub 6} analogues were produced for use as isotope-labeled internal standards. • Isotope-labeled standards compensate for ESI matrix effects in LC-MS/MS. • Femtomolar sensitivities and 93–108% quantitation accuracy were achieved for human fecal SCFAs. - Abstract: Short-chain fatty acids (SCFAs) are produced by anaerobic gut microbiota in the large bowel. Qualitative and quantitative measurements of SCFAs in the intestinal tract and the fecal samples are important to understand the complex interplay between diet, gut microbiota and host metabolism homeostasis. To develop a new LC-MS/MS method for sensitive and reliable analysis of SCFAs in human fecal samples, 3-nitrophenylhydrazine (3NPH) was employed for pre-analytical derivatization to convert ten C{sub 2}–C{sub 6} SCFAs to their 3-nitrophenylhydrazones under a single set of optimized reaction conditions and without the need of reaction quenching. The derivatives showed excellent in-solution chemical stability. They were separated on a reversed-phase C{sub 18} column and quantitated by negative-ion electrospray ionization – multiple-reaction monitoring (MRM)/MS. To achieve accurate quantitation, the stable isotope-labeled versions of the derivatives were synthesized in a single reaction vessel from {sup 13}C{sub 6}-3NPH, and were used as internal standard to compensate for the matrix effects in ESI. Method validation showed on-column limits of detection and quantitation over the range from low to high femtomoles for the ten SCFAs, and the intra-day and inter-day precision for determination of nine of the ten SCFAs in human fecal samples was ≤8.8% (n = 6). The quantitation accuracy ranged from 93.1% to 108.4% (CVs ≤ 4.6%, n = 6). This method was used to determine the SCFA concentrations and compositions in six human fecal samples. One of the six samples, which was collected from a

  3. Acanthocephalan fish parasites (Rhadinorhynchidae Lühe, 1912) as potential biomarkers: Molecular-chemical screening by pyrolysis-field ionization mass spectrometry

    Science.gov (United States)

    Kleinertz, S.; Eckhardt, K.-U.; Theisen, S.; Palm, H. W.; Leinweber, P.

    2016-07-01

    The present study represents the first molecular-chemical screening by pyrolysis-field ionization mass spectrometry applied on fish parasites. A total of 71 fishes from Balinese fish markets, 36 Auxis rochei (Risso, 1810) and 35 A. thazard (Lacepède, 1800), were studied for their acanthocephalan parasites. This is the first record of Rhadinorhynchus zhukovi in Balinese waters, Indonesia, and we describe for the first time A. rochei and A. thazard as R. zhukovi hosts. Using this method, small scale variations within the chemical compounds of acanthocephalans could be detected. Using this methodology it will be possible to generate additional, pollutant specific information from aquatic habitats in future with the potential of a new bioindicator application for parasite/host origin and/or environmental pollution.

  4. P-MaNGA Galaxies: emission-lines properties - gas ionization and chemical abundances from prototype observations

    Science.gov (United States)

    Belfiore, F.; Maiolino, R.; Bundy, K.; Thomas, D.; Maraston, C.; Wilkinson, D.; Sánchez, S. F.; Bershady, M.; Blanc, G. A.; Bothwell, M.; Cales, S. L.; Coccato, L.; Drory, N.; Emsellem, E.; Fu, H.; Gelfand, J.; Law, D.; Masters, K.; Parejko, J.; Tremonti, C.; Wake, D.; Weijmans, A.; Yan, R.; Xiao, T.; Zhang, K.; Zheng, T.; Bizyaev, D.; Kinemuchi, K.; Oravetz, D.; Simmons, A.

    2015-05-01

    MaNGA (Mapping Nearby Galaxies at Apache Point Observatory) is a 6-yr Sloan Digital Sky Survey (SDSS-IV) survey that will obtain spatially resolved spectroscopy from 3600 to 10 300 Å for a representative sample of over 10 000 nearby galaxies. In this paper, we present the analysis of nebular emission-line properties using observations of 14 galaxies obtained with P-MaNGA, a prototype of the MaNGA instrument. By using spatially resolved diagnostic diagrams, we find extended star formation in galaxies that are centrally dominated by Seyfert/LINER-like emission, which illustrates that galaxy characterizations based on single fibre spectra are necessarily incomplete. We observe extended low ionization nuclear emission-line regions (LINER)-like emission (up to 1Re) in the central regions of three galaxies. We make use of the Hα equivalent width [EW(Hα)] to argue that the observed emission is consistent with ionization from hot evolved stars. We derive stellar population indices and demonstrate a clear correlation between Dn(4000) and EW(HδA) and the position in the ionization diagnostic diagram: resolved galactic regions which are ionized by a Seyfert/LINER-like radiation field are also devoid of recent star formation and host older and/or more metal-rich stellar populations. We also detect extraplanar LINER-like emission in two highly inclined galaxies, and identify it with diffuse ionized gas. We investigate spatially resolved metallicities and find a positive correlation between metallicity and star formation rate surface density. We further study the relation between N/O versus O/H on resolved scales. We find that, at given N/O, regions within individual galaxies are spread towards lower metallicities, deviating from the sequence defined by galactic central regions as traced by Sloan 3-arcsec fibre spectra. We suggest that the observed dispersion can be a tracer for gas flows in galaxies: infalls of pristine gas and/or the effect of a galactic fountain.

  5. Constraining the sensitivity of iodide adduct chemical ionization mass spectrometry to multifunctional organic molecules using the collision limit and thermodynamic stability of iodide ion adducts

    Science.gov (United States)

    Lopez-Hilfiker, Felipe D.; Iyer, Siddarth; Mohr, Claudia; Lee, Ben H.; D'Ambro, Emma L.; Kurtén, Theo; Thornton, Joel A.

    2016-04-01

    The sensitivity of a chemical ionization mass spectrometer (ions formed per number density of analytes) is fundamentally limited by the collision frequency between reagent ions and analytes, known as the collision limit, the ion-molecule reaction time, and the transmission efficiency of product ions to the detector. We use the response of a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) to N2O5, known to react with iodide at the collision limit, to constrain the combined effects of ion-molecule reaction time, which is strongly influenced by mixing and ion losses in the ion-molecule reaction drift tube. A mass spectrometric voltage scanning procedure elucidates the relative binding energies of the ion adducts, which influence the transmission efficiency of molecular ions through the electric fields within the vacuum chamber. Together, this information provides a critical constraint on the sensitivity of a ToF-CIMS towards a wide suite of routinely detected multifunctional organic molecules for which no calibration standards exist. We describe the scanning procedure and collision limit determination, and we show results from the application of these constraints to the measurement of organic aerosol composition at two different field locations.

  6. Determination of polycyclic aromatic hydrocarbons in fractions in asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

    Science.gov (United States)

    Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

    2015-07-01

    An analytical method using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization for the determination of polycyclic aromatic hydrocarbons in asphalt fractions has been developed. The 14 compounds determined, characterized by having two or more condensed aromatic rings, are expected to be present in asphalt and are considered carcinogenic and mutagenic. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all of the compounds. The limits of detection ranged from 0.5 to 346.5 μg/L and the limits of quantification ranged from 1.7 to 1550 μg/L. The method was validated against a diesel particulate extract standard reference material (NIST SRM 1975), and the obtained concentrations agreed with the certified values. The method was applied to asphalt samples after its fractionation according to ASTM D4124 and the method of Green. The concentrations of the seven polycyclic aromatic hydrocarbons quantified in the sample ranged from 0.86 mg/kg for benzo[ghi]perylene to 98.32 mg/kg for fluorene. PMID:25885756

  7. Ultrapressure liquid chromatography-tandem mass spectrometry assay using atmospheric pressure photoionization (UPLC-APPI-MS/MS) for quantification of 4-methoxydiphenylmethane in pharmacokinetic evaluation.

    Science.gov (United States)

    Farhan, Nashid; Fitzpatrick, Sean; Shim, Yun M; Paige, Mikell; Chow, Diana Shu-Lian

    2016-09-01

    4-Methoxydiphenylmethane (4-MDM), a selective augmenter of Leukotriene A4 Hydrolase (LTA4H), is a new anti-inflammatory compound for potential treatment of chronic obstructive pulmonary disease (COPD). Currently, there is no liquid chromatography tandem mass spectrometric (LC-MS/MS) method for the quantification of 4-MDM. A major barrier for developing the LC-MS/MS method is the inability of electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) to ionize 4-MDM due to its hydrophobicity and lack of any functional group for ionization. With the advent of atmospheric pressure photoionization (APPI) technique, many hydrophobic compounds have been demonstrated to ionize by charge transfer reactions. In this study, a highly sensitive ultrapressure liquid chromatography tandem mass spectrometry assay using atmospheric pressure photoionization (UPLC-APPI-MS/MS) for the quantifications of 4-MDM in rat plasma has been developed and validated. 4-MDM was extracted from the plasma by solid phase extraction (SPE) and separated chromatographically using a reverse phase C8 column. The photoionization (PI) was achieved by introducing anisole as a dopant to promote the reaction of charge transfer. The assay with a linear range of 5 (LLOQ)-400ngmL(-1) met the regulatory requirements for accuracy, precision and stability. The validated assay was employed to quantify the plasma concentrations of 4-MDM after an oral dosing in Sprague Dawley (SD) rats. PMID:27232150

  8. The ionizing treatment of food

    International Nuclear Information System (INIS)

    This book of proceedings contains the talks given by the members of the Society of chemical experts of France (SECF) and by various specialists of the ionizing treatment during the scientific days of September 25-26, 1997. The aim of this meeting was to reconsider the effects of ionization from a scientific point of view and apart from the polemics generated by this domain. The following topics were discussed successively: source and characterization of a ionizing treatment, biological effects of ionization on food and the expected consequences, the ionizing treatment and the reduction of the vitamin C content of fruits and vegetables, is it safe to eat irradiated food?, the organoleptic modifications of food after ionization, quality assurance of dosimetry measurements in an industrial installation of food ionization, the French and European regulations in food ionization, the detection of irradiated foodstuffs, processed food and complex lipid matrices, sterilization of dishes for immuno-depressed patients using ionization. (J.S.)

  9. Organic chemical analysis on a microscopic scale using two-step laser desorption/laser ionization mass spectrometry

    Science.gov (United States)

    Kovalenko, L. J.; Philippoz, J.-M.; Bucenell, J. R.; Zenobi, R.; Zare, R. N.

    1991-01-01

    The distribution of PAHs in the Allende meteorite has been measured using two-step laser desorption and laser multiphoton-ionization mass spectrometry. This method enables in situ analysis (with a spatial resolution of 1 mm or better) of selected organic molecules. Results show that PAH concentrations are locally high compared to the average concentration found by analysis of pulverized samples, and are found primarily in the fine-grained matrix; no PAHs were detected in the interiors of individual chondrules at the detection limit (about 0.05 ppm).

  10. Microcrystalline silicon and the impact on micromorph tandem solar cells

    OpenAIRE

    Meier, Johannes; Dubail, S.; Golay, S.; Kroll, U.; Faÿ, Sylvie; Vallat-Sauvain, Evelyne; Feitknecht, Luc; Dubail, J.; Shah, Arvind

    2008-01-01

    Intrinsic microcrystalline silicon opens up new ways for silicon thin-film multi-junction solar cells, the most promising being the “micromorph” tandem concept. The microstructure of entirely microcrystalline p–i–n solar cells is investigated by transmission electron microscopy. By applying low pressure chemical vapor deposition ZnO as front TCO in p–i–n configurated micromorph tandems, a remarkable reduction of the microcrystalline bottom cell thickness is achieved. Micromorph tandem cells w...

  11. Targeted metabolomic analysis of Escherichia coli by desorption electrospray ionization and extractive electrospray ionization mass spectrometry.

    Science.gov (United States)

    Jackson, Ayanna U; Werner, Sean R; Talaty, Nari; Song, Yishu; Campbell, Karinna; Cooks, R Graham; Morgan, John A

    2008-04-15

    Desorption electrospray ionization (DESI) was utilized to monitor the presence of targeted central carbon metabolites within bacterial cell extracts and the quench supernatant of Escherichia coli. The targeted metabolites were identified through tandem mass spectrometry (MS/MS) product ion scans using collision-induced dissociation in the negative ion mode. Picogram detection limits were achieved for a majority of the metabolites during MS/MS analysis of standard metabolite solutions. In a [U-(13)C]glucose pulse experiment, where uniformly labeled glucose was fed to E. coli, the corresponding fragment ions from labeled metabolites in extracts were generally observed. There was evidence of matrix effects including moderate suppression by other metabolites within the spectra of the labeled and unlabeled extracts. To improve the specificity and sensitivity of detection, optimized in situ ambient chemical reactions using DESI and extractive electrospray ionization (EESI) were carried out for targeted compounds. This study provides the first indication of the potential to perform in situ targeted metabolomics of a bacterial sample via ambient ionization mass spectrometry. PMID:18243123

  12. Identification and Characterization of the Major Chemical Constituents in Fructus Akebiae by High-Performance Liquid Chromatography Coupled with Electrospray Ionization-Quadrupole-Time-of-Flight Mass Spectrometry.

    Science.gov (United States)

    Ling, Yun; Zhang, Qing; Zhu, Dan-dan; Chen, Fei; Kong, Xiu-hua; Liao, Liang

    2016-02-01

    Fructus Akebiae (FA), the dry fruit of Akebia quinata (THUNB.) DECNE., possesses potent antidepressant properties. Owing to the structural complexity, high polarity and thermal lability in plants, it is difficult and time-consuming to analyze the major chemical constituents by traditional strategies that involve extraction, isolation, purification and identification by chemical manipulations and spectroscopic methods. In this study, a high-performance liquid chromatography coupled with electrospray ionization-quadrupole-time-of-flight mass spectrometry (HPLC-ESI-Q-TOF-MS-MS) method was established for quickly identifying the chemical constituents in the extract of Fructus Akebiae. The main saponin components in the extract of Fructus Akebiae were detected with the HPLC-ESI-Q-TOF-MS-MS in negative-ion mode. These components were further analyzed by MS(2) spectra, and compared with the corresponding reference substances and literature data. Nineteen saponins in the extract of Fructus Akebiae were well separated in one run. The new method is accurate and rapid. It can be used to identify the main chemical constituents in the extract of Fructus Akebiae and can be suitable for the quality control of Fructus Akebiae. PMID:26311648

  13. Upgrading of the tandem

    International Nuclear Information System (INIS)

    The program of the tandem-linac accelerator system is summarized under the following headings: operating experience for the tandem, operation of the superconducting linac, upgrading of the tandem (ion sources, vacuum systems, terminal box, stripping foils, beam bunching), installation of the booster, planned accelerator system improvements, experimental facilities development at the super conducting-linac booster (new beam line, layout and installation of the 00 beam line in the new experiment area, beam optics calculations, 65-in. scattering chamber, split-pole spectrograph, sum/multiplicity detector, nuclear target making and development), and university use of the tandem accelerator

  14. Bacteriophage cell lysis of Shiga toxin-producing Escherichia coli for top-down proteomic identification of Shiga toxin 1 & 2 using matrix-assisted laser desorption/ionization tandem time-of-light mass spectrometry

    Science.gov (United States)

    RATIONALE: Analysis of bacteria by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) often relies upon sample preparation methods that result in cell lysis, e.g. bead-beating. However, Shiga toxin-producing Escherichia coli (STEC) can undergo bacteriophage...

  15. Application of high resolution Chemical Ionization Mass Spectrometry (CI-ToFMS to study SOA composition: focus on formation of oxygenated species via aqueous phase processing

    Directory of Open Access Journals (Sweden)

    D. Aljawhary

    2013-07-01

    Full Text Available This paper demonstrates the capabilities of Chemical Ionization Mass Spectrometry (CIMS to study secondary organic aerosol (SOA composition with a high resolution (HR time-of-flight mass analyzer (aerosol-CI-ToFMS. In particular, by studying aqueous oxidation of Water Soluble Organic Compounds (WSOC extracted from α-pinene ozonolysis SOA, we assess the capabilities of three common CIMS reagent ions: (a protonated water clusters (H2OnH+, (b acetate CH3C(OO− and (c iodide water clusters I(H2On− to monitor SOA composition. As well, we report the relative sensitivity of these reagent ions to a wide range of common organic aerosol constituents. We find that (H2OnH+ is more selective to the detection of less oxidized species, so that the range of O/C and OSC (carbon oxidation state in the SOA spectra is considerably lower than those measured using CH3C(OO− and I(H2On−. Specifically, (H2OnH+ ionizes organic compounds with OSC ≤ 1.3, whereas CH3C(OO− and I(H2On− both ionize highly oxygenated organics with OSC up to 4 with I(H2On− being more selective towards multi-functional organic compounds. In the bulk O/C and H/C space, i.e. in a Van Krevelen plot, there is a remarkable agreement in both absolute magnitude and oxidation trajectory between CI-ToFMS data and those from a high resolution aerosol mass spectrometer (HR-AMS. This indicates that the CI-ToFMS data captures much of the chemical change occurring in the particle and that gas phase species, which are not detected by the HR-AMS, do not dominate the overall ion signal. Finally, the data illustrate the capability of aerosol-CI-ToFMS to monitor specific chemical change, including the fragmentation and functionalization reactions that occur during organic oxidation, and the oxidative conversion of dimeric SOA species into monomers. Overall, aerosol-CI-ToFMS is a valuable, selective complement to some common SOA characterization methods, such as AMS and spectroscopic techniques. Both

  16. Calculation of aqueous solubility of crystalline un-ionized organic chemicals and drugs based on structural similarity and physicochemical descriptors.

    Science.gov (United States)

    Raevsky, Oleg A; Grigor'ev, Veniamin Yu; Polianczyk, Daniel E; Raevskaja, Olga E; Dearden, John C

    2014-02-24

    Solubilities of crystalline organic compounds calculated according to AMP (arithmetic mean property) and LoReP (local one-parameter regression) models based on structural and physicochemical similarities are presented. We used data on water solubility of 2615 compounds in un-ionized form measured at 25±5 °C. The calculation results were compared with the equation based on the experimental data for lipophilicity and melting point. According to statistical criteria, the model based on structural and physicochemical similarities showed a better fit with the experimental data. An additional advantage of this model is that it uses only theoretical descriptors, and this provides means for calculating water solubility for both existing and not yet synthesized compounds. PMID:24456022

  17. An evaluation of liquid chromatography/mass spectrometry with atmospheric pressure chemical ionization for the rapid and simultaneous measurement of carbamate pesticides and organophorus pesticides

    International Nuclear Information System (INIS)

    Liquid chromatography/mass spectrometry with an atmospheric pressure chemical ionization interface (LC/APCI/MS) is evaluated for the simultaneous determination of carbamate pesticides and organophosphorus pesticides in a single chromatographic analysis. APCI mass spectra of those compounds were obtained to study their ionization characteristics. APCI provided abundant ions such as protonated molecules and characteristic fragment ions for carbamate pesticides and organophosphorus pesticides. To evaluate the feasibility of the LC/APCI/MS for a routine quantitative analysis, the linearity and repeatability of LC/APCI/MS were examined by measuring standard solution mixtures of five carbamate pesticides and four organophosphorus pesticides over the range of 1 to 100 μg/mL. The peak areas in chromatograms of characteristic ions for those compounds showed less than 3% of variation from run to tun. The standard calibration curves for the nine pesticides show good linearity in the concentration range. The detection limits of the LC/APCI/MS system for those compounds range from 0.006 to 0.2 ng

  18. Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Bag, Soumabha; Hendricks, P.I. [Aston Labs, Department of Chemistry, Purdue University, West Lafayette, IN 47907 (United States); Reynolds, J.C. [Centre for Analytical Science, Loughborough University, Loughborough, Leicestershire (United Kingdom); Cooks, R.G., E-mail: cooks@purdue.edu [Aston Labs, Department of Chemistry, Purdue University, West Lafayette, IN 47907 (United States)

    2015-02-20

    Highlights: • In-situ derivatization and simultaneous ionization used to detect aldehydes. • Biogenic aliphatic and aromatic aldehydes reacted with 4-aminophenol. • Derivatized products yield structurally characteristic fragment ions. • This measurement demonstrated using a miniaturized portable mass spectrometer. - Abstract: Ionization of aliphatic and aromatic aldehydes is improved by performing simultaneous chemical derivatization using 4-aminophenol to produce charged iminium ions during paper spray ionization. Accelerated reactions occur in the microdroplets generated during the paper spray ionization event for the tested aldehydes (formaldehyde, n-pentanaldehyde, n-nonanaldehyde, n-decanaldehyde, n-dodecanaldehyde, benzaldehyde, m-anisaldehyde, and p-hydroxybenzaldehyde). Tandem mass spectrometric analysis of the iminium ions using collision-induced dissociation demonstrated that straight chain aldehydes give a characteristic fragment at m/z 122 (shown to correspond to protonated 4-(methyleneamino)phenol), while the aromatic aldehyde iminium ions fragment to give a characteristic product ion at m/z 120. These features allow straightforward identification of linear and aromatic aldehydes. Quantitative analysis of n-nonaldehyde using a benchtop mass spectrometer demonstrated a linear response over 3 orders of magnitude from 2.5 ng to 5 μg of aldehyde loaded on the filter paper emitter. The limit of detection was determined to be 2.2 ng for this aldehyde. The method had a precision of 22%, relative standard deviation. The experiment was also implemented using a portable ion trap mass spectrometer.

  19. Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry

    International Nuclear Information System (INIS)

    Highlights: • In-situ derivatization and simultaneous ionization used to detect aldehydes. • Biogenic aliphatic and aromatic aldehydes reacted with 4-aminophenol. • Derivatized products yield structurally characteristic fragment ions. • This measurement demonstrated using a miniaturized portable mass spectrometer. - Abstract: Ionization of aliphatic and aromatic aldehydes is improved by performing simultaneous chemical derivatization using 4-aminophenol to produce charged iminium ions during paper spray ionization. Accelerated reactions occur in the microdroplets generated during the paper spray ionization event for the tested aldehydes (formaldehyde, n-pentanaldehyde, n-nonanaldehyde, n-decanaldehyde, n-dodecanaldehyde, benzaldehyde, m-anisaldehyde, and p-hydroxybenzaldehyde). Tandem mass spectrometric analysis of the iminium ions using collision-induced dissociation demonstrated that straight chain aldehydes give a characteristic fragment at m/z 122 (shown to correspond to protonated 4-(methyleneamino)phenol), while the aromatic aldehyde iminium ions fragment to give a characteristic product ion at m/z 120. These features allow straightforward identification of linear and aromatic aldehydes. Quantitative analysis of n-nonaldehyde using a benchtop mass spectrometer demonstrated a linear response over 3 orders of magnitude from 2.5 ng to 5 μg of aldehyde loaded on the filter paper emitter. The limit of detection was determined to be 2.2 ng for this aldehyde. The method had a precision of 22%, relative standard deviation. The experiment was also implemented using a portable ion trap mass spectrometer

  20. 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 in...... variation for the analysis of the 12 different flavonoids in quality control urine samples were 12.3% on average (range 11.0-13.7%, n = 24, reproducibility) and the repeatability of the assay were 5.0% (mean, range 0.1-14.8%, it = 12). A subset of 10 urine samples from a human dietary intervention study...

  1. The effect of H2SO4 - amine clustering on chemical ionization mass spectrometry (CIMS) measurements of gas-phase sulfuric acid

    DEFF Research Database (Denmark)

    Kurten, T.; Petaja, T.; Smith, J.;

    2011-01-01

    chemistry. From the computational data, three conclusions can be drawn. First, a significant fraction of the gas-phase sulfuric acid molecules are very likely clustered with amines if the amine concentration is around or above a few ppt. Second, some fraction of these acid-amine clusters may not be charged...... by the CIMS instrument, though the most reliable computational methods employed predict this fraction to be small; on the order of ten percent or less. Third, the amine molecules will evaporate practically immediately after charging, thus evading detection. These effects may need to be taken into...... account in the interpretation of atmospheric measurement data obtained using chemical ionization methods. The purpose of this study is not to criticize the CIMS method, but to help understand the implications of the measured results....

  2. Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn for measuring organic acids in concentrated bulk aerosol – a laboratory and field study

    Directory of Open Access Journals (Sweden)

    J. Williams

    2012-08-01

    Full Text Available The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS at the boreal forest station SMEAR II at Hyytiälä, Finland, is demonstrated in this study. APCI is a soft ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was increased by a factor of 7.5 to 11 (e.g. ~40 ng m−3 for pinonic acid by using the miniature Versatile Aerosol Concentration Enrichment System (mVACES upstream of the mass spectrometer. The APCI-IT-MS was calibrated in the negative ion mode with two biogenic organic acid standards – pinic acid and pinonic acid. Pinic acid was used as a surrogate for the quantification of the total amount of organic acids in the ambient aerosol based on the total signal intensities in the negative ion mode. The results were compared with the total organic signal of a C-ToF-AMS during the HUMPPA-COPEC 2010 field campaign. The campaign average contribution of organic acids measured by APCI-IT-MS to the total sub-micron organic aerosol mass was estimated to be about 60%. Very good correlation between APCI-IT-MS and C-ToF-AMS (Pearson's R = 0.94 demonstrates soft ionization mass spectrometry as a complimentary technique to AMS with electron impact ionization. MS2 studies of specific m/z ratios recorded during the HUMPPA-COPEC 2010 field campaign were compared to MS2 studies of selected monoterpene oxidation products formed in simulation chamber experiments. The comparison of the resulting fragments shows that oxidation products of the main VOCs emitted at Hyytiälä (α-pinene and Δ3-carene cannot account for all of the measured fragments, which illustrates the complexity of ambient aerosol and possibly indicates unidentified or underestimated biogenic SOA precursor in the boreal forest.

  3. Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn for measuring organic acids in concentrated bulk aerosol – a laboratory and field study

    Directory of Open Access Journals (Sweden)

    J. Williams

    2013-02-01

    Full Text Available The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS at the boreal forest station SMEAR II at Hyytiälä, Finland, is demonstrated in this study. APCI is a soft-ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was improved by a factor of 7.5 to 11 (e.g. ∼40 ng m3 for pinonic acid by using the miniature versatile aerosol concentration enrichment system (mVACES upstream of the mass spectrometer. The APCI-IT-MS was calibrated in the negative ion mode with two biogenic organic acid standards – pinic acid and pinonic acid. Pinic acid was used as a surrogate for the quantification of the total amount of organic acids in the ambient aerosol based on the total signal intensities in the negative ion mode. The results were compared with the total organic signal of a C-ToF-AMS during the HUMPPA-COPEC 2010 field campaign. The campaign average contribution of organic acids measured by APCI-IT-MS to the total submicron organic aerosol mass was estimated to be about 60%, based on the response of pinic acid. Very good correlation between APCI-IT-MS and C-ToF-AMS (Pearson's R = 0.94 demonstrates soft-ionization mass spectrometry as a complimentary technique to AMS with electron impact ionization. MS2 studies of specific m/z ratios recorded during the HUMPPA-COPEC 2010 field campaign were compared to MS2 studies of selected monoterpene oxidation products formed in simulation chamber experiments. The comparison of the resulting fragments shows that oxidation products of the main VOCs emitted at Hyytiälä (α-pinene and Δ3-carene cannot account for all of the measured fragments. Possible explanations for those unaccounted fragments are the presence of unidentified or underestimated biogenic SOA precursors, or that different products are formed by a

  4. Determination of oxygen and nitrogen derivatives of polycyclic aromatic hydrocarbons in fractions of asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

    Science.gov (United States)

    Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

    2015-12-01

    Liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization was used for the determination of polycyclic aromatic hydrocarbon derivatives, the oxygenated polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons, formed in asphalt fractions. Two different methods have been developed for the determination of five oxygenated and seven nitrated polycyclic aromatic hydrocarbons that are characterized by having two or more condensed aromatic rings and present mutagenic and carcinogenic properties. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all compounds. The detection limits of the methods ranged from 0.1 to 57.3 μg/L for nitrated and from 0.1 to 6.6 μg/L for oxygenated derivatives. The limits of quantification were in the range of 4.6-191 μg/L for nitrated and 0.3-8.9 μg/L for oxygenated derivatives. The methods were validated against a diesel particulate extract standard reference material (National Institute of Standards and Technology SRM 1975), and the obtained concentrations (two nitrated derivatives) agreed with the certified values. The methods were applied in the analysis of asphalt samples after their fractionation into asphaltenes and maltenes, according to American Society for Testing and Material D4124, where the maltenic fraction was further separated into its basic, acidic, and neutral parts following the method of Green. Only two nitrated derivatives were found in the asphalt sample, quinoline and 2-nitrofluorene, with concentrations of 9.26 and 2146 mg/kg, respectively, whereas no oxygenated derivatives were detected. PMID:26446274

  5. Laboratory and Ambient Measurements of Oxidized Organic Compounds in the Gas Phase Using Nitrate Ion Chemical Ionization Coupled with High Resolution Time-of-Flight Mass Spectrometry

    Science.gov (United States)

    Massoli, P.; Stark, H.; Canagaratna, M. R.; Krechmer, J.; Lambe, A. T.; Isaacman-VanWertz, G. A.; Nowak, J. B.; Kimmel, J.; Kroll, J. H.; Jayne, J. T.; Worsnop, D. R.

    2015-12-01

    Chemical Ionization Mass Spectrometry (CIMS) is a widely used technique for molecular level characterization of inorganic and organic gas phase species. Here we present laboratory and ambient measurements of gaseous organic compounds by means of a High Resolution Time-of-Flight Chemical Ionization Mass Spectrometry (HR-ToF-CIMS) using nitrate ion (NO3-) chemistry, which recently has proven capable of selectively detecting oxidized organic molecules in the gas-phase via clustering with NO3- and its high order clusters. Such low and extremely low volatility organic compounds (LVOC, ELVOC) have an important role in particulate phase chemistry and formation of secondary organic aerosol (SOA). The HR-ToF-CIMS was deployed during the Southern Oxidant and Aerosol Study (SOAS) at the forest site in Centreville, AL (June 1 - July 15, 2013), where emissions were dominated by biogenic volatile organic compounds (BVOC), occasionally mixing with anthropogenic emissions. During SOAS, the HR-ToF-CIMS detected oxidation products of both isoprene (typically C5 LVOC) and terpenes (typically C10 ELVOC). The isoprene-related LVOC showed a diurnal cycle with a day time peak, while two groups of terpene ELVOC were identified, one peaking at night and one peaking during the day. Positive Matrix Factorization (PMF) analyses are applied to the dataset to further interpret these observations. The effect of anthropogenic pollution on the biogenic-dominated environment was also investigated during periods of elevated nitrous and sulfur dioxide levels. To further aid in interpretation of the SOAS dataset, oxidized organic molecules were produced via OH and O3 initiated oxidation of biogenic gas-phase precursors in targeted laboratory studies and detected using the HR-ToF-CIMS. Spectra were obtained in these studies over a range of simulated atmospheric conditions.

  6. Chemical actions of ionizing radiation on oligopeptide derivatives of glycine in the neutral (Zwitterion) and basic forms

    Energy Technology Data Exchange (ETDEWEB)

    Garrison, W.M.; Sokol, H.A.

    1980-01-01

    Effects of protonation of the terminal NH/sub 2/ group on the relative yields of reductive deamination and deamidation by e/sup -/ in the ..gamma..-radiolysis of di, tri and tetra glycine in the solid state are described. The experimental data provide direct chemical evidence of specific sites of addition of e/sup -/ to c = o bonds along the peptide chain.

  7. Production of Arq+ ions with a tandem linear Paul trap

    International Nuclear Information System (INIS)

    A tandem linear Paul trap was used to create highly charged Argon ions by electron impact ionizations. By improving the operation scheme, the production of Ar4+ ions was confirmed. Possible improvements for the future experiments with laser cooled Ca+ ions are suggested

  8. Observations and Modeling of the Green Ocean Amazon 2014/15: Hydroxyl Radical (OH) Chemical Ionization Mass Spectrometer (CIMS) Field Campaign Report

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Saewung [Univ. of California, Irvine, CA (United States)

    2016-05-01

    The University of California, Irvine, science team (Dr. Saewung Kim, Dr. Roger Seco, Dr. Alex Guenther, and Dr. Jim Smith) deployed a chemical ionization mass spectrometer system for hydroxyl radical (OH) and sulfuric acid quantifications. As part of the GoAmazon 2014/15 field campaign. Hydroxyl radical determines tropospheric oxidation capacity and had been expected to be very low in the pristine rain forest region such as the Brazilian Amazon because of the presence of significant levels of highly reactive biogenic volatile organic compounds and very low levels of NO, which is an OH recycling agent. However, several recent in situ OH observations provided by a laser-induced fluorescence system reported unaccountably high OH concentrations. To address this discrepancy, a series of laboratory and theoretical studies has postulated chemical reaction mechanisms of isoprene that may regenerate OH in photo-oxidation processes. Along with these efforts, potential artifacts on the laser induced fluorescence system from isoprene and its oxidation products also have been explored. Therefore, the first chemical ionization mass spectrometer observations at the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility’s T3 site in Manacapuru, Brazil, are expected to provide a critical experimental constraint to address uncertainty in constraining oxidation capacity over pristine rain forest environments. In addition, we deployed a National Center for Atmospheric Research (NCAR) proton transfer reaction time-of-flight mass spectrometer to characterize atmospheric volatile organic compound levels, especially isoprene and its oxidation products, which are critical input parameters for box modeling to simulate OH with different isoprene photo-oxidation schemes. As there has been no report on noticeable new particle formation events, our first in situ sulfuric acid observations in the Amazon rain forest were expected to constrain the

  9. Chemical analysis of raw and processed Fructus arctii by high-performance liquid chromatography/diode array detection-electrospray ionization-mass spectrometry

    Directory of Open Access Journals (Sweden)

    Kunming Qin

    2014-01-01

    Full Text Available Background: In traditional Chinese medicine (TCM, raw and processed herbs are used to treat the different diseases. Fructus Arctii, the dried fruits of Arctium lappa l. (Compositae, is widely used in the TCM. Stir-frying is the most common processing method, which might modify the chemical compositions in Fructus Arctii. Materials and Methods: To test this hypothesis, we focused on analysis and identification of the main chemical constituents in raw and processed Fructus Arctii (PFA by high-performance liquid chromatography/diode array detection-electrospray ionization-mass spectrometry. Results: The results indicated that there was less arctiin in stir-fried materials than in raw materials. however, there were higher levels of arctigenin in stir-fried materials than in raw materials. Conclusion: We suggest that arctiin reduced significantly following the thermal conversion of arctiin to arctigenin. In conclusion, this finding may shed some light on understanding the differences in the therapeutic values of raw versus PFA in TCM.

  10. Chlorine activation by N2O5: simultaneous, in situ detection of ClNO2 and N2O5 by chemical ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    J. A. Thornton

    2009-01-01

    Full Text Available We report a new method for the simultaneous in situ detection of nitryl chloride (ClNO2 and dinitrogen pentoxide (N2O5 using chemical ionization mass spectrometry (CIMS. The technique relies on the formation and detection of iodide ion-molecule clusters, I(ClNO2− and I(N2O5−. The novel N2O5 detection scheme is direct. It does not suffer from high and variable chemical interferences, which are associated with the typical method of nitrate anion detection. We address the role of water vapor, electric field strength, and instrument zero determinations, which influence the overall sensitivity and detection limit of this method. For both species, the method demonstrates high sensitivity (>1 Hz/pptv, precision (~10% for 100 pptv in 1 s, and accuracy (~20%, the latter ultimately determined by the nitrogen dioxide (NO2 cylinder calibration standard and characterization of inlet effects. For the typically low background signals (<10 Hz and high selectivity, we estimate signal-to-noise (S/N ratios of 2 for 1 pptv in 60 s averages, but uncertainty associated with the instrumental zero currently leads to an ultimate detection limit of ~5 pptv for both species. We validate our approach for the simultaneous in situ measurement of ClNO2 and N2O5 while on board the Research Vessel (RV Knorr as part of the ICEALOT 2008 Field Campaign.

  11. Chlorine activation by N2O5: simultaneous, in situ detection of ClNO2 and N2O5 by chemical ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    J. A. Thornton

    2009-05-01

    Full Text Available We report a new method for the simultaneous in situ detection of nitryl chloride (ClNO2 and dinitrogen pentoxide (N2O5 using chemical ionization mass spectrometry (CIMS. The technique relies on the formation and detection of iodide ion-molecule clusters, I(ClNO2− and I(N2O5−. The novel N2O5 detection scheme is direct. It does not suffer from high and variable chemical interferences, which are associated with the typical method of nitrate anion detection. We address the role of water vapor, CDC electric field strength, and instrument zero determinations, which influence the overall sensitivity and detection limit of this method. For both species, the method demonstrates high sensitivity (>1 Hz/pptv, precision (~10% for 100 pptv in 1 s, and accuracy (~20%, the latter ultimately determined by the nitrogen dioxide (NO2 cylinder calibration standard and characterization of inlet effects. For the typically low background signals (S/N ratios of 2 for 1 pptv in 60 s averages, but uncertainty associated with the instrumental zero currently leads to an ultimate detection limit of ~5 pptv for both species. We validate our approach for the simultaneous in situ measurement of ClNO2 and N2O5 while on board the R/V Knorr as part of the ICEALOT 2008 Field Campaign.

  12. Quantification of low levels of organochlorine pesticides using small volumes (≤100 μl) of plasma of wild birds through gas chromatography negative chemical ionization mass spectrometry

    International Nuclear Information System (INIS)

    A solid phase extraction and gas chromatography with negative chemical ionization mass spectrometry in scan mode (GC-NCI-MS) method was developed to identify and quantify for the first time low levels of organochlorine pesticides (OCs) in plasma samples of less than 100 μl from wild birds. The method detection limits ranged from 0.012 to 0.102 pg/μl and the method reporting limit from 0.036 to 0.307 pg/μl for α, γ, β and δ-hexachlorocyclohexane (HCH), heptachlor, aldrin, heptachlor epoxide, endosulfan I, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p,p'-DDE), dieldrin, endrin, endosulfan-II, endrin-aldehyde and endosulfan-sulfate. Pesticide levels in small serum samples from individual Falco sparverius, Sturnella neglecta, Mimus polyglottos and Columbina passerina were quantified. Concentrations ranged from not detected (n/d) to 204.9 pg/μl for some OC pesticides. All levels in the food web in and around cultivated areas showed the presence of pesticides notwithstanding the small areas for agriculture existing in the desert of Baja California peninsula. - This technique allows small birds to be used as indicators of chemical contamination in habitats because pesticides can be quantified in very small volumes of plasma

  13. Investigation into effects of ionizing radiations on physical-chemical properties of bulgarian sorts of peaches and grapes

    International Nuclear Information System (INIS)

    The aim of this study was to ascertain the degree and direction of those changes in physicochemical characteristics of irradiated peaches and grapes which determine their quality after irradiation and during storage. The following main conclusions are made: irradiation with doses of 200 to 300 krad does not cause significant alterations in the chemical composition and physicochemical characteristics of peaches and grapes; irradiation has a direct effect on the consistancy of peaches and grapes, leading to their softening which is proportional to the radiation dose used; radiation treatment is advisable in the case of peaches and grapes in tended for short-term rather than long-term storage at low temperatures

  14. Chemical Ionization Mass Spectrometry-Based Measurements of HO2 and RO2 During TRACE-P

    Science.gov (United States)

    Cantrell, Christopher A.; Eisele, Fred L.

    2004-01-01

    The Transport and Chemical Evolution over the Pacific (TRACE-P) mission extends NASA's Global Tropospheric Experiment (GTE) series of campaigns. TRACE-P was an aircraft-based campaign that was part of a larger ground-based and aircraft-based program (APARE) under the auspices of the International Global Atmospheric Chemistry (IGAC) program. TRACE-P was designed to (1) determine the chemical composition of Asian outflow over the western Pacific, and to (2) determine the chemical evolution of the Asian outflow. These objectives were addressed through a variety of observations and numerical modeling exercises. In particular, the goals included sampling strategies that would improve understanding of the budgets of odd hydrogen species (OH and HO2), budgets of NOx (NO, NO2, and their reservoirs), and impacts of oxidants produced in the outflow on air quality in the United States. The NASA DC-8 and P-3B aircraft were deployed in the March and April, 2001 out of primary bases of operation in Hong Kong and Yokota Air Base in Japan. These two aircraft have complementary capabilities which allow high altitude and long range impacts, as well as low altitude, local impacts to be assessed. In order to quantify the composition and evolution of Asian outflow, it is important to quantify as many species as possible including photochemically active species (e.g. NO2, CH2O, O3, acetone, etc.), sources species (VOCs, CO, NOx, SO2, aerosols), reactive intermediates including free radicals (OH, HO2, RO2, and their reservoirs), and end products (nitric acid, sulfuric acid, secondary aerosols, etc.). The more complete the measurement suite, the more tightly constrained the numerical modeling can be (within the uncertainties of the measurements). The numerical models range in sophistication from simple steady state box models (as employed in this study) to multi-dimensional chemical transport models. Data were collected on approximately 20 flights of the DC-8 and 21 flights of the P-3B

  15. Comprehensive chemical profiling of guizhi fuling capsule by the combined use of gas chromatography-mass spectrometry with a deconvolution software and rapid-resolution liquid chromatography quadrupole time-of-flight tandem mass spectrometry.

    Science.gov (United States)

    Wang, Ya-Qiong; Qi, Lian-Wen; Aa, Jiye; Wang, Guang-Ji; Gao, Wen; Cheng, Shu-Jie; Wang, Zhen-Zhong; Xiao, Wei; Li, Ping

    2012-10-01

    Herbal formulations are complex natural mixtures. Researchers usually tend to focus more on analysis of nonvolatile components but pay less attention to volatile compounds. In this study, an analytical strategy combining two approaches was established for comprehensive analysis of herbal formulations. Guizhi Fuling capsule (GFC), a drug approved by the FDA to enter phase II clinical trial for treatment of primary dysmenorrhea, was taken as a case for analysis. Gas chromatography-mass spectrometry (GC-MS) with automated mass spectral deconvolution and identification system (AMDIS) led to rapid identification of 48 volatile components including four acetophenones, three fatty acid esters, 13 phenylpropanoids and 19 sesquiterpenes. Most of them were found from Guizhi. The volatile oils of Guizhi have been proved to exhibit many pharmacological activities. This is helpful in understanding the pharmacological mechanism of GFC. Furthermore, AMDIS turned out to be efficient and reliable for analysis of complex herbal formulations. Rapid-resolution liquid chromatography (RRLC) coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (ESI-Q-TOF MS/MS) allowed the identification of 70 nonvolatile components including six acetophenones, 12 galloyl glucoses, 31 monoterpene glycosides, three phenols and 12 triterpene acids. Fragmentation behaviors of assigned components, especially triterpene acids, which are hard to identify by low-resolution MS, were first investigated by TOF MS/MS. Characteristic ions and typical loss of assigned triterpene acids were summarized. Combinatorial use of GC-MS-AMDIS and RRLC-ESI-Q-TOF MS/MS could be of great help in global qualitative analysis of GFC, as well as other herbal products. PMID:22297903

  16. Characterization of Organic Nitrate Formation in Limonene Secondary Organic Aerosol using High-Resolution Chemical Ionization Mass Spectrometry

    Science.gov (United States)

    Faxon, Cameron; Hammes, Julia; Peng, Jianfei; Hallquist, Mattias; Pathak, Ravi

    2016-04-01

    Previous work has shown that organic nitrates (RONO2) are prevalent in the boundary layer, and can contribute significantly to secondary organic aerosol formation. Monoterpenes, including limonene, have been shown to be precursors for the formation of these organic nitrates. Limonene has two double bonds, either of which may be oxidized by NO3 or O3. This leads to the generation of products that can subsequently condense or partition into the particle phase, producing secondary organic aerosol. In order to further elucidate the particle and gas phase product distribution of organic nitrates forming from the reactions of limonene and the nitrate radical (NO3), a series of experiments were performed in the Gothenburg Flow Reactor for Oxidation Studies at Low Temperatures (G-FROST), described by previous work. N2O5 was used as the source for NO3 and NO2, and a characterized diffusion source was used to introduce limonene into the flow reactor. All experiments were conducted in the absence of light, and the concentration of limonene was increased step-wise throughout each experiment to modify the ratio of N2O5to limonene. The experiments were conducted such that both limonene- and N2O5-limited regimes were present. Gas and particle phase products were measured using an iodide High-Resolution Time-of-Flight Mass Spectrometer (HR-ToF-CIMS) coupled to a Filter Inlet for Gases and AEROsols (FIGAERO, and particle size and SOA mass concentrations were derived using a Scanning Mobility Particle Sizer (SMPS). CIMS measurement techniques have previously been employed for the measurement of organic nitrate products of such compounds using multiple reagent ions. The use of this instrumentation allowed for the identification of chemical formulas for gas and particle phase species. The findings from the experiments will be presented in terms of the relative gas-particle partitioning of major products and the effects of N2O5/limonene ratios on product distributions. Additionally, a

  17. Tandem mobile robot system

    Science.gov (United States)

    Buttz, James H.; Shirey, David L.; Hayward, David R.

    2003-01-01

    A robotic vehicle system for terrain navigation mobility provides a way to climb stairs, cross crevices, and navigate across difficult terrain by coupling two or more mobile robots with a coupling device and controlling the robots cooperatively in tandem.

  18. Quantitation of triacylglycerols in edible oils by off-line comprehensive two-dimensional liquid chromatography-atmospheric pressure chemical ionization mass spectrometry using a single column.

    Science.gov (United States)

    Wei, Fang; Hu, Na; Lv, Xin; Dong, Xu-Yan; Chen, Hong

    2015-07-24

    In this investigation, off-line comprehensive two-dimensional liquid chromatography-atmospheric pressure chemical ionization mass spectrometry using a single column has been applied for the identification and quantification of triacylglycerols in edible oils. A novel mixed-mode phenyl-hexyl chromatographic column was employed in this off-line two-dimensional separation system. The phenyl-hexyl column combined the features of traditional C18 and silver-ion columns, which could provide hydrophobic interactions with triacylglycerols under acetonitrile conditions and can offer π-π interactions with triacylglycerols under methanol conditions. When compared with traditional off-line comprehensive two-dimensional liquid chromatography employing two different chromatographic columns (C18 and silver-ion column) and using elution solvents comprised of two phases (reversed-phase/normal-phase) for triacylglycerols separation, the novel off-line comprehensive two-dimensional liquid chromatography using a single column can be achieved by simply altering the mobile phase between acetonitrile and methanol, which exhibited a much higher selectivity for the separation of triacylglycerols with great efficiency and rapid speed. In addition, an approach based on the use of response factor with atmospheric pressure chemical ionization mass spectrometry has been developed for triacylglycerols quantification. Due to the differences between saturated and unsaturated acyl chains, the use of response factors significantly improves the quantitation of triacylglycerols. This two-dimensional liquid chromatography-mass spectrometry system was successfully applied for the profiling of triacylglycerols in soybean oils, peanut oils and lord oils. A total of 68 triacylglycerols including 40 triacylglycerols in soybean oils, 50 triacylglycerols in peanut oils and 44 triacylglycerols in lord oils have been identified and quantified. The liquid chromatography-mass spectrometry data were analyzed

  19. Highly sensitive isotope-dilution liquid-chromatography-electrospray ionization-tandem-mass spectrometry approach to study the drug-mediated modulation of dopamine and serotonin levels in Caenorhabditis elegans.

    Science.gov (United States)

    Schumacher, Fabian; Chakraborty, Sudipta; Kleuser, Burkhard; Gulbins, Erich; Schwerdtle, Tanja; Aschner, Michael; Bornhorst, Julia

    2015-11-01

    Dopamine (DA) and serotonin (SRT) are monoamine neurotransmitters that play a key role in regulating the central and peripheral nervous system. Their impaired metabolism has been implicated in several neurological disorders, such as Parkinson's disease and depression. Consequently, it is imperative to monitor changes in levels of these low-abundant neurotransmitters and their role in mediating disease. For the first time, a rapid, specific and sensitive isotope-dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated for the quantification of DA and SRT in the nematode Caenorhabditis elegans (C. elegans). This model organism offers a unique approach for studying the effect of various drugs and environmental conditions on neurotransmitter levels, given by the conserved DA and SRT biology, including synaptic release, trafficking and formation. We introduce a novel sample preparation protocol incorporating the usage of sodium thiosulfate in perchloric acid as extraction medium that assures high recovery of the relatively unstable neurotransmitters monitored. Moreover, the use of both deuterated internal standards and the multiple reaction monitoring (MRM) technique allows for unequivocal quantification. Thereby, to the best of our knowledge, we achieve a detection sensitivity that clearly exceeds those of published DA and SRT quantification methods in various matrices. We are the first to show that exposure of C. elegans to the monoamine oxidase B (MAO-B) inhibitor selegiline or the catechol-O-methyltransferase (COMT) inhibitor tolcapone, in order to block DA and SRT degradation, resulted in accumulation of the respective neurotransmitter. Assessment of a behavioral output of the dopaminergic system (basal slowing response) corroborated the analytical LC-MS/MS data. Thus, utilization of the C. elegans model system in conjunction with our analytical method is well-suited to investigate drug-mediated modulation of the DA and

  20. Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn) for measuring organic acids in concentrated bulk aerosol – a laboratory and field study

    OpenAIRE

    Williams, J.; Kulmala, M.; D. R. Worsnop; Junninen, H.; Petäjä, T.; Ehn, M.; Brüggemann, M; M. Äijälä; Vogel, A. L.; Hoffmann, T.

    2013-01-01

    The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) at the boreal forest station SMEAR II at Hyytiälä, Finland, is demonstrated in this study. APCI is a soft-ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was improved by a factor of 7.5 to 11 (e.g. ∼40 ng m3 for pinonic acid) b...

  1. Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn) for measuring organic acids in concentrated bulk aerosol – a laboratory and field study

    OpenAIRE

    Williams, J.; Kulmala, M.; D. R. Worsnop; Junninen, H.; Petäjä, T.; Ehn, M.; Brüggemann, M; M. Äijälä; Vogel, A. L.; Hoffmann, T.

    2012-01-01

    The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) at the boreal forest station SMEAR II at Hyytiälä, Finland, is demonstrated in this study. APCI is a soft ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was increased by a factor of 7.5 to 11 (e.g. ~40 ng m−3 for pinonic ac...

  2. Radioactive beams produced by the ISOL method: development for laser ionization and for surface ionization

    International Nuclear Information System (INIS)

    The works were carried out in the framework of the research program PARRNe (production of radioactive neutron-rich nuclei). This program aims to determine optimal conditions to produce intense beams of neutron-rich isotopes. This thesis treats multiple technical aspects related to the production of separate radioactive isotopes in line (ISOL). It deals mainly with the development of the target-source unit which is the key element for projects such as SPIRAL-2 or EURISOL.The first part presents the various methods using fission as production mode and compares them: fission induced by thermal neutrons, induced by fast neutrons and photofission. The experiment carried out at CERN validated the interest of the photofission as a promising production mode of radioactive ions. That is why the institute of nuclear physics of Orsay decided to build a linear electron accelerator at the Tandem d'Orsay (ALTO).The second part of this thesis deals with the development of uranium targets. The X-rays diffraction and Scanning Electron Microscopy have been used as analysis techniques. They allowed to determine the chemical and structural characteristics of uranium carbide targets as function of various heating temperatures. After the production, the process of ionization has been studied. Two types of ion source have been worked out: the first one is a surface ion source and the second one is a source based on resonant ionization by laser. These two types of sources will be used for the ALTO project. (author)

  3. Identification of known chemicals and their metabolites from Alpinia oxyphylla fruit extract in rat plasma using liquid chromatography/tandem mass spectrometry (LC-MS/MS) with selected reaction monitoring.

    Science.gov (United States)

    Chen, Feng; Li, Hai-Long; Tan, Yin-Feng; Li, Yong-Hui; Lai, Wei-Yong; Guan, Wei-Wei; Zhang, Jun-Qing; Zhao, Yuan-Sheng; Qin, Zhen-Miao

    2014-08-01

    Alpinia oxyphylla (Yizhi) capsularfruits are commonly used in traditional medicine. Pharmacological studies have demonstrated that A. oxyphylla capsularfruits have some beneficial roles. Besides volatile oil, sesquiterpenes, diarylheptanoids and flavonoids are main bioactive constituents occurring in the Yizhi capsularfruits. The representative constituents include tectochrysin, izalpinin, chrysin, apigenin-4',7-dimethylether, kaempferide, yakuchinone A, yakuchinone B, oxyphyllacinol and nootkatone. Their content levels in the fruit and its pharmaceutical preparations have been reported by our group. The nine phytochemicals are also the major components present in the Yizhi alcoholic extracts, which have anti-diarrheal activities. However, the fates of these constituents in the body after oral or intravenous administration remain largely unknown. In the present study, we focus on these phytochemicals albeit other concomitant compounds. The chemicals and their metabolites in rat plasma were identified using liquid chromatography/tandem mass spectrometry with selected reaction monitoring mode after orally administered Yizhi extract to rats. Rat plasma samples were treated by methanol precipitation, acidic or enzymatic hydrolysis. This target analysis study revealed that: (1) low or trace plasma levels of parent chemicals were measured after p.o. administration of Yizhi extract, Suoquan capsules and pills to rats; (2) flavonoids and diarylheptanoids formed mainly monoglucuronide metabolites; however, diglucuronide metabolites for chrysin, izalpinin and kaempferide were also detected; (3) metabolic reduction of Yizhi diarylheptanoids occurred in rats. Yakuchinone B was reduced to yakuchinone A and then to oxyphyllacinol in a stepwise manner and subsequently glucuronidated by UDP-glucuronosyl transferase. Further research is needed to characterize the UDP-glucuronosyl transferase and reductase involved in the biotransformation of Yizhi chemicals. PMID:24879483

  4. Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry.

    Science.gov (United States)

    Bag, Soumabha; Hendricks, P I; Reynolds, J C; Cooks, R G

    2015-02-20

    Ionization of aliphatic and aromatic aldehydes is improved by performing simultaneous chemical derivatization using 4-aminophenol to produce charged iminium ions during paper spray ionization. Accelerated reactions occur in the microdroplets generated during the paper spray ionization event for the tested aldehydes (formaldehyde, n-pentanaldehyde, n-nonanaldehyde, n-decanaldehyde, n-dodecanaldehyde, benzaldehyde, m-anisaldehyde, and p-hydroxybenzaldehyde). Tandem mass spectrometric analysis of the iminium ions using collision-induced dissociation demonstrated that straight chain aldehydes give a characteristic fragment at m/z 122 (shown to correspond to protonated 4-(methyleneamino)phenol), while the aromatic aldehyde iminium ions fragment to give a characteristic product ion at m/z 120. These features allow straightforward identification of linear and aromatic aldehydes. Quantitative analysis of n-nonaldehyde using a benchtop mass spectrometer demonstrated a linear response over 3 orders of magnitude from 2.5 ng to 5 μg of aldehyde loaded on the filter paper emitter. The limit of detection was determined to be 2.2 ng for this aldehyde. The method had a precision of 22%, relative standard deviation. The experiment was also implemented using a portable ion trap mass spectrometer. PMID:25682245

  5. The use of ionizing radiations in the treatment of liquid and solid waste; biological and physico-chemical effects and industrial study

    International Nuclear Information System (INIS)

    Short recycling of waste water and the use of liquid or dehydrated sludge as natural manure for agriculture, or animal supplement feed is of great economical and ecological interest. However, it requires strong disinfection. Treatment with ionizing radiation can be used as a complement to conventional methods in the treatment of liquid and solid wastes. An experiment conducted with a high-energy electron beam linear accellerator (10 MeV) is presented. Degradation of undesirable metabolites in wastes occurs at a dose of 50 krad. Undesirable seeds, present in sludge, are destroyed with a 200-krad dose. The same dose is sufficient for parasitic and bacterial disinfection (DL 90). Destruction of poliovirus (DL 90) is obtained at 400 krad. Higher doses (1000-2000 krad) produce mineralisation of toxic organic mercury or reduce some toxic chemical pollutants present in sludge and improve flocculation. Industrial study shows that waste treatment with high-energy electron beams is technically and economically feasible. The design for a treatment unit of 5 MCi cobalt-equivalent, with a capacity of 500 t/Mrad/24h is presented, with indicative cost calculation

  6. Quantification of trace fatty acid methyl esters in diesel fuel by using multidimensional gas chromatography with electron and chemical ionization mass spectrometry.

    Science.gov (United States)

    Webster, R L; Rawson, P M; Evans, D J; Marriott, P J

    2016-07-01

    Measurement of contamination of marine and naval diesel fuels (arising from product mixing or adulteration) with biodiesel or fatty acid methyl esters can be problematic, especially at very low levels. A suitable solution for this task for trace amounts of individual fatty acid methyl esters with resolution and quantification can be achieved by using a multidimensional gas chromatographic approach with electron and chemical ionization mass spectrometric detection. A unique column set comprising a 100 m methyl-siloxane nonpolar first dimension column and high-temperature ionic liquid column in the second dimension enabled identification of individual fatty acid methyl esters at below the lowest concentrations required to be reported in a diesel fuel matrix. Detection limits for individual fatty acid methyl esters compounds ranged from 0.5 to 5.0 mg/L, with excellent linearity up to 5000 mg/L and repeatability of the method from 1.3 to 3.2%. The method was applied to the analysis of diesel fuel samples with suspected biodiesel contamination. Contamination at 568 mg/L was calculated for an unknown sample and interpretation of the results permitted the determination of a likely source of the contamination. PMID:27159197

  7. Characterization of gamma-irradiated polyethylene terephthalate by liquid-chromatography-mass-spectrometry (LC-MS) with atmospheric-pressure chemical ionization (APCI)

    International Nuclear Information System (INIS)

    Low-molecular-weight (low-MW) constituents of polyethylene terephthalate (PET), irradiated with 6Co gamma rays at 25 and 50 kGy, were analyzed by HPLC-MS with atmospheric-pressure chemical ionization (APCI). Consistent with earlier results, the concentrations of the major compounds that are present in the non-irradiated PET do not change perceptibly. However, we find a small but significant increase in terephthalic acid ethylester, from less than 1 mg/kg in the non-irradiated control to ca. 2 mg/kg after 50 kGy, which has not been described before. The finding is important because it gives an impression of the sensitivity of the analytical method. Additionally, it shows that even very radiation-resistant polymers can form measurable amounts of low-MW radiolysis products. The potential and limitations of LC-MS for the analysis of radiolysis products and unidentified migrants are briefly discussed in the context of the question: How can we validate our analytical methods for unknown analytes?

  8. Quantification of low levels of organochlorine pesticides using small volumes (chemical ionization mass spectrometry.

    Science.gov (United States)

    Rivera-Rodríguez, Laura B; Rodríguez-Estrella, Ricardo; Ellington, James Jackson; Evans, John J

    2007-07-01

    A solid phase extraction and gas chromatography with negative chemical ionization mass spectrometry in scan mode (GC-NCI-MS) method was developed to identify and quantify for the first time low levels of organochlorine pesticides (OCs) in plasma samples of less than 100 microl from wild birds. The method detection limits ranged from 0.012 to 0.102 pg/microl and the method reporting limit from 0.036 to 0.307 pg/microl for alpha, gamma, beta and delta-hexachlorocyclohexane (HCH), heptachlor, aldrin, heptachlor epoxide, endosulfan I, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p,p'-DDE), dieldrin, endrin, endosulfan-II, endrin-aldehyde and endosulfan-sulfate. Pesticide levels in small serum samples from individual Falco sparverius, Sturnella neglecta, Mimus polyglottos and Columbina passerina were quantified. Concentrations ranged from not detected (n/d) to 204.9 pg/microl for some OC pesticides. All levels in the food web in and around cultivated areas showed the presence of pesticides notwithstanding the small areas for agriculture existing in the desert of Baja California peninsula. PMID:17240024

  9. Determination of the mycotoxin moniliformin in cultures of Fusarium subglutinans and in naturally contaminated maize by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    Science.gov (United States)

    Sewram, V; Nieuwoudt, T W; Marasas, W F; Shephard, G S; Ritieni, A

    1999-07-01

    A LC-MS method employing triethylamine as ion-pairing reagent for the determination of moniliformin in culture material and naturally contaminated maize samples is described. Mass spectrometric detection of moniliformin was accomplished following atmospheric pressure chemical ionization to yield the deprotonated molecular ion [M-H]- at m/z 97. The moniliformin response was found to be linear over the injected range 10 ng to 700 ng and a detection limit of 10 ng was attainable at a signal-to-noise (S/N) ratio of 4. Five South African strains of Fusarium subglutinans were grown on maize kernels and moniliformin extracted with an acetonitrile-water (95:5) mixture. Following sample clean up with reversed-phase (C18) solid-phase extraction cartridges, the extracts were subjected to LC-MS analysis. Triethylamine was used as an ion-pair reagent and found to improve the retention characteristics of moniliformin without any detrimental effects to the instrument. Moniliformin concentrations ranged between 130 mg/kg and 1460 mg/kg culture. Application of this method to naturally contaminated maize samples from Transkei showed that it was capable of measuring moniliformin levels down to 10 micrograms/kg in selected moldy maize cobs. This is the first report on the application of LC-MS to the analysis of moniliformin in cultures of F. subglutinans and in naturally contaminated maize. PMID:10427758

  10. Atmospheric measurements of gas-phase HNO3 and SO2 using chemical ionization mass spectrometry during the MINATROC field campaign 2000 on Monte Cimone

    Directory of Open Access Journals (Sweden)

    B. Bunz

    2002-11-01

    Full Text Available The EU-project MINATROC (MINeral dust And TROpospheric Chemistry aims at enabling an estimation of the influence of mineral dust, a major, but to date largely ignored component of tropospheric aerosol, on tropospheric oxidant cycles. Within the scope of this project continuous atmospheric measurements of gas-phase HNO3 and SO2 were conducted in June and July 2000 at the CNR WMO station, situated on Monte Cimone (MTC (44° 11' N -- 10° 42' E, 2165 m asl, Italy. African air transporting dust is occasionally advected over the Mediterranean Sea to the site, thus mineral aerosol emitted from Africa will encounter polluted air masses and provide ideal conditions to study their interactions. HNO3 and SO2 were measured with an improved CIMS (chemical ionization mass spectrometry system for ground-based measurements that was developed and built at MPI-K Heidelberg. Since HNO3 is a very sticky compound special care was paid for the air-sampling and background-measurement system. Complete data sets could be obtained before, during and after major dust intrusions. For the first time these measurements might provide a strong observational indication of efficient uptake of gas-phase HNO3 by atmospheric mineral-dust aerosol particles.

  11. The role of physical and chemical properties of Pd nanostructured materials immobilized on inorganic carriers on ion formation in atmospheric pressure laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Silina, Yuliya E; Koch, Marcus; Volmer, Dietrich A

    2014-06-01

    Fundamental parameters influencing the ion-producing efficiency of palladium nanostructures (nanoparticles [Pd-NP], nanoflowers, nanofilms) during laser irradiation were studied in this paper. The nanostructures were immobilized on the surface of different solid inorganic carrier materials (porous and mono-crystalline silicon, anodic porous aluminum oxide, glass and polished steel) by using classical galvanic deposition, electroless local deposition and sputtering. It was the goal of this study to investigate the influence of both the nanoparticular layer as well as the carrier material on ion production for selected analyte molecules. Our experiments demonstrated that the dimensions of the synthesized nanostructures, the thickness of the active layers, surface disorders, thermal conductivity and physically or chemically adsorbed water influenced signal intensities of analyte ions during surface-assisted laser desorption/ionization (SALDI) while no effects such as plasmon resonance, photoelectric effect or catalytic activity were expected to occur. Excellent LDI abilities were seen for Pd-NPs immobilized on steel, while Pd nanoflowers on porous silicon exhibited several disadvantages; viz, strong memory effects, dependency of the analytical signal on amount of physically and chemically adsorbed water inside porous carrier, reduced SALDI activity from unstable connections between Pd and semiconductor material, decrease of the melting point of pure silicon after Pd immobilization and resulting strong laser ablation of metal/semiconductor complex, as well as significantly changed surface morphology after laser irradiation. The analytical performance of Pd-NP/steel was further improved by applying a hydrophobic coating to the steel surface before galvanic deposition. This procedure increased the distance between Pd-NPs, thus reducing thermal stress upon LDI; it simultaneously decreased spot sizes of deposited sample solutions. PMID:24913399

  12. Ionization detector

    International Nuclear Information System (INIS)

    A novel ionization detector for use in X-ray tomography is described in detail. To achieve the ultimate resolution, the use of small detectors is necessary and, for ionization detectors, this implies using xenon gas at high pressure. Conventional small detectors can suffer from ''bowing'' but the present design overcomes their problems. (U.K.)

  13. Ambient ionization mass spectrometry: A tutorial

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Min-Zong; Cheng, Sy-Chi; Cho, Yi-Tzu [Department of Chemistry, National Sun Yat-Sen University, Kaohsiung, Taiwan (China); Shiea, Jentaie, E-mail: jetea@fac.nsysu.edu.tw [Department of Chemistry, National Sun Yat-Sen University, Kaohsiung, Taiwan (China); Cancer Center, Kaohsiung Medical University, Kaohsiung, Taiwan (China)

    2011-09-19

    Highlights: {yields} Ambient ionization technique allows the direct analysis of sample surfaces with little or no sample pretreatment. {yields} We sort ambient ionization techniques into three main analytical strategies, direct ionization, direct desorption/ionization, and two-step ionization. {yields} The underlying principles of operation, ionization processes, detecting mass ranges, sensitivity, and representative applications of these techniques are described and compared. - Abstract: Ambient ionization is a set of mass spectrometric ionization techniques performed under ambient conditions that allows the direct analysis of sample surfaces with little or no sample pretreatment. Using combinations of different types of sample introduction systems and ionization methods, several novel techniques have been developed over the last few years with many applications (e.g., food safety screening; detection of pharmaceuticals and drug abuse; monitoring of environmental pollutants; detection of explosives for antiterrorism and forensics; characterization of biological compounds for proteomics and metabolomics; molecular imaging analysis; and monitoring chemical and biochemical reactions). Electrospray ionization and atmospheric pressure chemical ionization are the two main ionization principles most commonly used in ambient ionization mass spectrometry. This tutorial paper provides a review of the publications related to ambient ionization techniques. We describe and compare the underlying principles of operation, ionization processes, detecting mass ranges, sensitivity, and representative applications of these techniques.

  14. High-Performance Liquid Chromatography with Diode Array Detector and Electrospray Ionization Ion Trap Time-of-Flight Tandem Mass Spectrometry to Evaluate Ginseng Roots and Rhizomes from Different Regions.

    Science.gov (United States)

    Wang, Hong-Ping; Zhang, You-Bo; Yang, Xiu-Wei; Yang, Xin-Bao; Xu, Wei; Xu, Feng; Cai, Shao-Qing; Wang, Ying-Ping; Xu, Yong-Hua; Zhang, Lian-Xue

    2016-01-01

    Ginseng, Panax ginseng C. A. Meyer, is an industrial crop in China and Korea. The functional components in ginseng roots and rhizomes are characteristic ginsenosides. This work developed a new high-performance liquid chromatography coupled with electrospray ionization ion trap time-of-flight multistage mass spectrometry (LC-ESI-IT-TOF-MS(n)) method to identify the triterpenoids. Sixty compounds (1-60) including 58 triterpenoids were identified from the ginseng cultivated in China. Substances 1, 2, 7, 15-20, 35, 39, 45-47, 49, 55-57, 59, and 60 were identified for the first time. To evaluate the quality of ginseng cultivated in Northeast China, this paper developed a practical liquid chromatography-diode array detection (LC-DAD) method to simultaneously quantify 14 interesting ginsenosides in ginseng collected from 66 different producing areas for the first time. The results showed the quality of ginseng roots and rhizomes from different sources was different due to growing environment, cultivation technology, and so on. The developed LC-ESI-IT-TOF-MS(n) method can be used to identify many more ginsenosides and the LC-DAD method can be used not only to assess the quality of ginseng, but also to optimize the cultivation conditions for the production of ginsenosides. PMID:27171066

  15. Fast throughput determination of 21 allergenic disperse dyes from river water using reusable three-dimensional interconnected magnetic chemically modified graphene oxide followed by liquid chromatography-tandem quadrupole mass spectrometry.

    Science.gov (United States)

    Zhao, Yong-Gang; Li, Xiao-Ping; Yao, Shan-Shan; Zhan, Ping-Ping; Liu, Jun-Chao; Xu, Chang-Ping; Lu, Yi-Yu; Chen, Xiao-Hong; Jin, Mi-Cong

    2016-01-29

    We report the template-free fabrication of three-dimensional hierarchical nanostructures, i.e., three-dimensional interconnected magnetic chemically modified graphene oxide (3D-Mag-CMGO), through a simple and low-cost self-assembly process using one-pot reaction based on solvothermal method. The excellent properties of the 3D-Mag-CMGO are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), vibrating sample magnetometer (VSM), FTIR, elementary analyzer (EA) and X-ray photoelectron spectroscopy (XPS). The easiness-to-handle of the magnetic dispersive solid phase extraction (Mag-dSPE) procedure is developed for preconcentration of 21 allergenic disperse dyes from river water. The obtained results show the higher extraction capacity of 3D-Mag-CMGO with recoveries between 80.0-112.0%. Furthermore, an ultra-fast liquid chromatography-tandem quadrupole mass spectrometry (UFLC-MS/MS) method for determination of 21 allergenic disperse dyes in river at sub-ppt levels has been developed with pretreatment of the samples by Mag-dSPE. The limits of quantification (LOQs) for the allergenic disperse dyes are between 0.57-34.05ng/L. Validation results on linearity, specificity, trueness and precision, as well as on application to the analysis of 21 allergenic disperse dyes in fifty real samples demonstrate the applicability to environment monitoring analysis. PMID:26777090

  16. Ionization detector

    International Nuclear Information System (INIS)

    The objects of the invention are, first, to provide an ionization detector having a three chamber structure characterised by a built-in feedback path that regeneratively stabilizes the operating point of the detector. Secondly, to provide a specially designed chamber construction including electrodes shaped so as to enhance the efficiency of the chamber and reduce ion recombination. The ionization chamber described has a chamber structure with a first closed chamber and a second chamber able to receive gases from outside. These two chambers have a common boundary including a common electrode. One electrode associated with the second chamber, and one within the first chamber, define a third chamber within the first chamber allowing an ionization path between. A radioactive source provides ionizing radiation for all three chambers and establishes an ionization current. There is a detector coupled to the common electrode for detecting changes in this current. (U.K.)

  17. Development of a High-Resolution H3O+ Chemical Ionization Mass Spectrometer for Gas-phase Hydrocarbons and its Application During the 2015 SONGNEX Aircraft Campaign

    Science.gov (United States)

    Koss, A.; Yuan, B.; De Gouw, J. A.; Warneke, C.; Stark, H.

    2015-12-01

    In-situ time-of-flight chemical ionization mass spectrometers (ToF-CIMS) using H3O+ reagent ion chemistry (PTR-MS) are a relatively new technique in detection of gas-phase hydrocarbons, and recent improvements in instrument sensitivity, mass resolution, and ease of field deployment have expanded their use in atmospheric chemistry. The comparatively low-energy H3O+ ionization technique is ideal for measuring complex mixtures of hydrocarbons, and, compared to conventional quadrupole PTRMS, the newest generation of ToF-CIMS measure many more species simultaneously and with a sensitivity that is as high as a quadrupole PTR-MS. We describe here the development of a commercially available ToF CIMS into an H3O+CIMS suitable for deployment on aircraft, and its application during an aircraft campaign studying emissions from oil and natural gas extraction industry. We provide an overview of instrument development and specifications, including design, characterization, and field operation. We then discuss data processing and interpretation. First, we investigate determination of intensities of poorly resolved peaks. The mass resolution of the present instrument (m/Δm ~4500) enables separate analysis of many isobaric peaks, but peaks are also frequently not fully resolved. Using results from laboratory tests, we quantify how the accuracy can be limited by the overlap in neighboring peaks, and compare to theoretical predictions from literature. We then briefly describe our method for quality assurance of reported compounds, and correction for background and humidity effects. Finally, we present preliminary results from the first field deployment of this instrument during the Spring 2015 SONGNEX aircraft campaign. This campaign sampled emissions from oil and natural gas extraction regions and associated infrastructure in the Western and Central United States. We will highlight results that illustrate (1) new scientific capability from improved mass resolution, which

  18. Validation of a Liquid Chromatography-Electrospray Ionization-Tandem Mass Spectrometry Method for Determination of All-Trans Retinoic Acid in Human Plasma and Its Application to a Bioequivalence Study

    Directory of Open Access Journals (Sweden)

    Jing-Bo Peng

    2014-01-01

    Full Text Available A sensitive, reliable and specific LC-MS-MS method was developed and validated for the identification and quantitation of all-trans retinoic acid (ATRA in human plasma. Acitretin was used as the internal standard (IS. After liquid-liquid extraction of 500 μL plasma with methyl tert-butyl ether (MTBE, ATRA and the IS were chromatographed on a HyPURITY C18 column (150 mm × 2.1 mm, 5 μm with the column temperature set at 40 °C. The mobile phase was consisted of 40% phase A (MTBE–methanol–acetic acid, 50:50:0.5, v/v and 60% phase B (water–methanol–acetic acid, 50:50:0.5, v/v with a flow rate of 0.3 mL/min. The API 4000 triple quadrupole mass spectrometer was operated in multiple reaction monitoring (MRM mode via the positive electrospray ionization interface using the transition m/z 301.4 → 123.1 for ATRA and m/z 326.9 → 177.1 for IS, respectively. The calibration curve was linear over the range of 0.45–217.00 ng/mL (r ≥ 0.999 with a lower limit of quantitation (LLOQ of 0.45 ng/mL. The intra- and inter-day precisions values were below 8% relative standard deviation and the accuracy was from 98.98% to 106.19% in terms of relative error. The validated method was successfully applied in a bioequivalence study of ATRA in Chinese healthy volunteers.

  19. Green processes for the extraction of bioactives from Rosemary: Chemical and functional characterization via ultra-performance liquid chromatography-tandem mass spectrometry and in-vitro assays.

    Science.gov (United States)

    Herrero, M; Plaza, M; Cifuentes, A; Ibáñez, E

    2010-04-16

    In this contribution, the performance of three different extraction procedures towards the extraction of antioxidants from rosemary (Rosmarinus officinalis) is presented. Namely, pressurized liquid extraction (PLE), using water and ethanol as solvents, supercritical fluid extraction (SFE), using neat CO(2) and supercritical CO(2) modified with ethanol, as well as a novel extraction process called Water Extraction and Particle formation On-line (WEPO) are directly compared. Different extraction conditions including temperatures, times and pressures have been studied. The produced extracts have been characterized in terms of extraction yield, antioxidant activity (using the DPPH radical scavenging method) and total phenols (using the Folin method). Besides, all the extracts have been chemically characterized using a new quantitative UPLC-MS/MS method. This method allowed the determination of the main antioxidants present in rosemary, including, among others, rosmarinic acid, carnosic acid and carnosol, attaining detection limits as low as 2ng/mL. The results obtained in this study show that PLE using ethanol at high temperatures (200 degrees C) was able to produce extracts with high antioxidant activity (EC(50) 8.8microg/mL) and high yield (ca. 40%) while efficiently extracting antioxidants of diverse polarity, among them, carnosic and rosmarinic acids, regarded as the most important antioxidants present in rosemary. Nevertheless, in this work, the ability of the three studied environmentally friendly extraction techniques to obtain bioactives from natural sources is demonstrated. PMID:19945706

  20. The effect of H2SO4 – amine clustering on chemical ionization mass spectrometry (CIMS) measurements of gas-phase sulfuric acid

    OpenAIRE

    Worsnop, D.R.; Mauldin, L.; Vehkamäki, H.; M. Ehn; Junninen, H.; Sipilä, M.; Ortega, I.K.; Smith,J; T. Petäjä; Kurtén, T.; M. Kulmala

    2011-01-01

    The state-of-the art method for measuring atmospheric gas-phase sulfuric acid is chemical ionization mass spectrometry (CIMS) based on nitrate reagent ions. We have assessed the possible effect of the sulfuric acid molecules clustering with base molecules on CIMS measurements using computational chemistry. From the computational data, three conclusions can be drawn. First, a significant fraction of the gas-phase sulfuric acid molecules are very likely clustered with amines if the amine concen...

  1. A field-deployable, chemical ionization time-of-flight mass spectrometer: application to the measurement of gas-phase organic and inorganic acids

    Directory of Open Access Journals (Sweden)

    T. H. Bertram

    2011-03-01

    Full Text Available We report a new field-deployable chemical ionization time-of-flight mass spectrometer (CI-TOFMS for the direct measurement of trace gases in the atmosphere. We apply the technique to the measurement of gas-phase inorganic and organic acids via negative-ion proton transfer, using acetate as the reagent ion. A novel high pressure interface, incorporating two RF-only quadrupoles is used to efficiently focus ions through four stages of differential pumping before analysis with a compact TOFMS. The high ion-duty cycle (>20% of the TOFMS, coupled to efficient production and transmission of ions in the high pressure interface results in a highly sensitive (>300 ions s−1 pptv−1 instrument capable of the fast measurement of atmospheric gases at trace levels. We demonstrate the efficient transfer and detection of both bare ions and ion-molecule clusters, and characterize the instrument during field measurements aboard the R/V Atlantis as part of the CalNex campaign during the spring of 2010. The in-field short-term precision is better than 5% at 1 pptv (pL/L, for 1-second averages. The detection limit (3σ, 1-second averages of the current version of the CI-TOFMS, as applied to the in situ detection of gas-phase acids, is limited by the magnitude and variability in the background determination and was determined to be 4 pptv.

  2. Gas chromatography/atmospheric pressure chemical ionization/mass spectrometry for the analysis of organochlorine pesticides and polychlorinated biphenyls in human serum.

    Science.gov (United States)

    Geng, Dawei; Jogsten, Ingrid Ericson; Dunstan, Jody; Hagberg, Jessika; Wang, Thanh; Ruzzin, Jerome; Rabasa-Lhoret, Rémi; van Bavel, Bert

    2016-07-01

    A method using a novel atmospheric pressure chemical ionization source for coupling gas chromatography (GC/APCI) to triple quadrupole mass spectrometry (MS/MS) for the determination of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) regulated by the Stockholm Convention is presented. One microliter injection of a six-point calibration curve of native PCBs and OCPs, ranging from 0.04 to 300pg/μL, was performed. The relative standard deviation (RSD) of the relative response factors (RRFs) was less than 15% with a coefficient of determination (r(2))>0.995. Meanwhile, two calibration solutions (CS), CS 2 (0.4pg/μL) and CS 3 (4pg/μL) were analyzed to study the repeatability calculated for both area and RRFs. The RSD for RRF ranged from 3.1 to 16% and 3.6 to 5.5% for CS 2 and CS 3, respectively. The limits of detection (LOD) determined by peak-to-peak signal-to-noise ratio (S/N) of 3 were compared between the GC/APCI/MS/MS and a GC coupled to high resolution mass spectrometry (GC/HRMS) system. GC/APCI/MS/MS resulted in lower LOD for most of the compounds, except for PCB#74, cis-chlordane and trans-chlordane. GC/APCI/MS/MS and GC/HRMS were also compared by performing analysis on 75 human serum samples together with eight QA/QC serum samples. The comparison between GC/APCI/MS/MS system and GC/HRMS system for 16 of the targeted compounds was carried out. No statistically significant difference was discovered. Due to increased sensitivity and user friendly operation under atmospheric pressure, GC/APCI/MS/MS is a powerful alternative technique that can easily meet the specification of GC/HRMS. PMID:27236485

  3. Comparative anti-inflammatory activities of curcumin and tetrahydrocurcumin based on the phenolic O-H bond dissociation enthalpy, ionization potential and quantum chemical descriptor.

    Science.gov (United States)

    Murakami, Yukio; Ishii, Hiroaki; Takada, Naoki; Tanaka, Shoji; Machino, Mamoru; Ito, Shigeru; Fujisawa, Seiichiro

    2008-01-01

    Curcumin and its reduced derivative tetrahydrocurcumin have been shown to exhibit chemopreventive activity. Cyclooxygenase-2 (COX-2) inhibition in lipopolysaccharide (LPS)- or Porphyromonas gingivalis fimbria-stimulated RAW 264.7 cells was investigated using Northern blot analysis. The fimbria-stimulated expression of the COX-2 gene was inhibited by curcumin but not by tetrahydrocurcumin. LPS-stimulated COX-2 gene expression was completely inhibited by curcumin, but an increase in the concentration of tetrahydrocurcumin did not cause complete inhibition of COX-2 expression. The inhibitory effect of curcumin on nuclear factor kappa B (NF-kappaB) activation in the cells was clearly observed, but that of tetrahydrocurcumin was incomplete even at a concentration of 20 microM. To explain the difference in effect between the two compounds, analysis of the frontier orbital was performed using ab initio 6-31G* wave function. The calculated chemical hardness (eta) for curcumin was clearly smaller, whereas its electronegativity (chi) and electrophilicity (omega) were clearly greater than the corresponding values for the curcumin-related compounds tetrahydrocurcumin, isoeugenol and eugenol. This suggested that the anti-inflammatory activities of curcumin may be related to eta-, chi- and/or omega-controlled enzymes. In addition, the bond dissociation enthalpy (BDE) of the phenolic OH was calculated using the density function theory (DFT)/B3LY. The total BDE values of curcumin and tetrahydrocurcumin were almost identical, but the BDE of one-electron oxidation and ionization potential (IP) for curcumin were lower than those for tetrahydrocurcumin, suggesting the highly pro-oxidative activity of curcumin. Curcumin has both oxidant and antioxidant properties. A causal link between the anti-inflammatory activities and molecular properties of phenolic antioxidants is suggested. PMID:18507010

  4. Quantum Chemical Benchmark Studies of the Electronic Properties of the Green Fluorescent Protein Chromophore. 1. Electronically Excited and Ionized States of the Anionic Chromophore in the Gas Phase.

    Science.gov (United States)

    Epifanovsky, Evgeny; Polyakov, Igor; Grigorenko, Bella; Nemukhin, Alexander; Krylov, Anna I

    2009-07-14

    We present the results of quantum chemical calculations of the electronic properties of the anionic form of the green fluorescent protein chromophore in the gas phase. The vertical detachment energy of the chromophore is found to be 2.4-2.5 eV, which is below the strongly absorbing ππ* state at 2.6 eV. The vertical excitation of the lowest triplet state is around 1.9 eV, which is below the photodetachment continuum. Thus, the lowest bright singlet state is a resonance state embedded in the photodetachment continuum, whereas the lowest triplet state is a regular bound state. Based on our estimation of the vertical detachment energy, we attribute a minor feature in the action spectrum as due to the photodetachment transition. The benchmark results for the bright ππ* state demonstrated that the scaled opposite-spin method yields vertical excitation within 0.1 eV (20 nm) from the experimental maximum at 2.59 eV (479 nm). We also report estimations of the vertical excitation energy obtained with the equation-of-motion coupled cluster with the singles and doubles method, a multireference perturbation theory corrected approach MRMP2 as well as the time-dependent density functional theory with range-separated functionals. Expanding the basis set with diffuse functions lowers the ππ* vertical excitation energy by 0.1 eV at the same time revealing a continuum of "ionized" states, which embeds the bright ππ* transition. PMID:26610014

  5. Measurements of Oxidized Organic Compounds during SOAS 2013 using nitrate ion chemical ionization coupled with High Resolution Time-of-Flight Mass Spectrometry

    Science.gov (United States)

    Massoli, P.; Stark, H.; Cnagaratna, M.; Junninen, H.; Hakala, J. P.; Mauldin, R.; Ehn, M.; Sipila, M.; Krechmer, J.; Kimmel, J.; Jimenez, J. L.; Jayne, J. T.; Worsnop, D. R.

    2013-12-01

    We present ambient measurements of gaseous organic compounds by means of a High Resolution Time-of-Flight Chemical Ionization Mass Spectrometry (HR-ToF-CIMS) using nitrate ion (NO3-) chemistry. This technique allows to selectively detect oxidized gas-phase species, e.g., oxidized organic molecules and sulfuric acid via clustering with NO3- and its high order clusters. The capability of making such measurements is important because both sulfuric acid and organic gas molecules have a recognized key role in new particle formation (NPF) processes and likely have an important role in particulate phase chemistry and formation of secondary organic aerosols (SOA). The HR-ToF-CIMS was deployed during the Southern Oxidant and Aerosol Study (SOAS) at the forest supersite in Centreville, AL, from June 1 to July 15, 2013. The main goal of the SOAS campaign was to investigate the composition and sources of SOA in the Southeast US, where emissions are mainly represented by biogenic volatile organic compounds (BVOC) emissions and in less extent by anthropogenic emissions (AVOC). During SOAS, the HR-ToF-CIMS detected a range of organic ions that based on previous literature could be identified as oxidation products of both isoprene and terpenes. The isoprene products were 5 to 10 times more abundant than the terpene products. The isoprene-related molecules showed a diurnal cycle with a day time peak, typically after 1500 local time, while the terpene products were higher at night (between 2000 and 0600 local time). These results are consistent with the diurnal trends of primary BVOC emissions from other co-located instruments. The ambient data are also compared to laboratory measurements where oxidized organic vapors are produced using a Potential Aerosol Mass (PAM) flow reactor by the OH oxidation of biogenic gas-phase precursors (isoprene, a-pinene) over multiple days of equivalent atmospheric exposure.

  6. Chemical ionization mass spectrometry of indol-3yl-acetic acid and cis-abscisic acid: evaluation of negative ion detection and quantification of cis-abscisic acid in growing maize roots

    International Nuclear Information System (INIS)

    Mass spectra of the derivatives of indol-3yl-acetic acid and cis-abscisic acid were obtained in electron impact and chemical ionization positive ion and negative ion modes. The respective merits of methane, isobutane, and ammonia as reagent gases for structure determination and sensitive detection were compared using the methyl esters. From one to 10 fluorine atoms were attached to IAA to improve the electron-capturing properties of the molecule. The best qualitative information was obtained when using positive ion chemical ionization with methane. However, the most sensitive detection, with at least two ions per molecule, was achieved by electron impact on the IAA-HFB-ME derivative and by negative ion chemical ionization with NH3 on the ABA-methyl ester derivative. p ]Quantitative analyses of ABA in different parts of maize (Zea mays cv. LG 11) root tips were performed by the latter technique. It was found that the cap and apex contained less ABA than the physiologically older parts of the root such as the elongation zone and the more differentiated tissues. This technique was also used to show a relation between maize root growth and the endogenous ABA level of the elongation zone and root tip: there is more ABA in the slowly growing roots than in the rapidly growing ones. (author)

  7. Tandem mirror fusion research

    International Nuclear Information System (INIS)

    The tandem mirror program has evolved considerably in the last decade. Of significance is the viable reactor concept embodied in the MARS design. An aggressive experimental program, culminating in the operation of MFTF-B in late 1986, will provide a firm basis for refining the MARS design as necessary for constructing a reactor prototype in the 1990s

  8. Chlorine activation by N2O5: simultaneous, in situ detection of ClNO2 and N2O5 by chemical ionization mass spectrometry

    OpenAIRE

    Thornton, J. A.; Kercher, J. P.; T. P. Riedel

    2009-01-01

    We report a new method for the simultaneous in situ detection of nitryl chloride (ClNO2) and dinitrogen pentoxide (N2O5) using chemical ionization mass spectrometry (CIMS). The technique relies on the formation and detection of iodide ion-molecule clusters, I(ClNO2)− and I(N2O5)−. The novel N2O5 detection scheme is direct. It does not suffer from high and variable chemical interferences, which are associated with the typical method of nitrate anion detection. We address the role o...

  9. Analysis of 1,2-diol diesters in vernix caseosa by high-performance liquid chromatography with atmospheric pressure chemical ionization mass spectrometry

    Czech Academy of Sciences Publication Activity Database

    Cvačka, Josef; Šubčíková, L.; Vrkoslav, Vladimír; Hoskovec, Michal; Míková, Radka; Čmelíková, T.

    Puerto de la Cruz : Universidad de La Laguna, 2013. s. 258-258. [ITP 2013. International Symposium on Electro- and Liquid Phase- Separation Techniques /20./. 06.10.2013-09.10.2013, Puerto de la Cruz] R&D Projects: GA ČR GAP206/12/0750 Institutional support: RVO:61388963 Keywords : lipids * lipidomics * tandem mass spectrometry Subject RIV: CB - Analytical Chemistry, Separation

  10. Peroxynitric acid (HO2NO2 measurements during the UBWOS 2013 and 2014 studies using iodide ion chemical ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    P. R. Veres

    2015-02-01

    Full Text Available Laboratory work is reported here establishing iodide ion chemical ionization mass spectrometry (I− CIMS as a sensitive method for the unambiguous detection of peroxynitric acid (HO2NO2, PNA. A~dynamic calibration source for HO2NO2, HO2, and HONO was developed and calibrated using a~novel total NOy detector (NOy CaRDS. Photochemical sources of these species were used for the calibration and validation of the I− CIMS instrument for detection of HO2NO2. A dual inlet system was developed to determine differences in the instrument response when using a heated inlet dissociator (150 °C and a "cold" room-temperature inlet. HO2NO2 was detected as I-HO2− (m/z 160, NO3− (m/z 62 and I-HO2NO2− (m/z 206. The I− CIMS normalized sensitivity to peroxynitric acid was 2.0 Hz pptv−1 with a detection limit (3σ of 40 pptv via detection of the I-HO2− (m/z 160 cluster ion using an inlet dissociator at a temperature of 150 °C. Alternatively, PNA was detected via I− CIMS with a cold inlet at both the NO3− (m/z 62 and I-HO2NO2− (m/z 206 ions with normalized detection sensitivities of 144 and 0.4 Hz pptv−1 respectively. The cold inlet sensitivity of iodide CIMS towards the detection of HO2 radicals, also via detection at the I-HO2− cluster ion, a potential HO2NO2 interference, was approximately 2.6 Hz pptv−1 with an instrumental detection limit (3σ of 20 pptv. Ambient observations of HO2NO2 using I− CIMS were made during the 2013 and 2014 Uintah Basin Wintertime Ozone Study (UBWOS are presented. Strong inversions leading to a build-up of many primary and secondary pollutants as well as low temperatures drove daytime HO2NO2 as high as 1.5 ppbv during the 2013 study. A comparison of HO2NO2 observations to mixing ratios predicted using a chemical box model describing an ozone formation event observed during the 2013 wintertime shows agreement in the daily maxima HO2NO2 mixing ratio, but a significant difference os several hours in the timing

  11. Ionizing radiation effects of Cobalt-60 on the physical-chemical, sensorial and microbiological of bread with addition of linseed (Linum usitatissimum)

    International Nuclear Information System (INIS)

    The incorporation of functional ingredients on breading products has grown very much lately, because of the preoccupation with the consumers' health. The linseed has awakened the interest by its high level of fiber, lignin, omega-3 and antioxidants compounds. The objective of the present work is evaluate the ionizing radiation effect of 60Co on the physical-chemical, sensorial and microbiological characteristics of bread with addition of different concentration of brown linseed. There were elaborated 3 types of bread: French roll, form bread prepared with the mixture and form bread produced with conventional ingredients. It was added smashed brown linseed on the bread dough, with concentrations of 8% and 12%. After the preparation, the three kinds of bread packed with polypropylene packages and taken to the IPEN/USP (Institute of Nuclear Energetic Research/University of São Paulo) and irradiated with doses of 6, 8 and 10 kGy. Treatments were elaborated without the addition of linseed and without irradiation, for control, totalizing 12 distinct treatments, to each bread formula tested. Chemical analyses were made (centesimal composition, anti-nutritional compounds, anti-oxidant activity, glycemic index, fat acids, complex B vitamins and minerals); physical analyses (cooking index, volume, color and water activity); sensorial analyses (preference tests and Descriptive Quantitative Analysis - ADQ); microbiological analysis and a survey about irradiated products. It could be seen that the addition of linseed was efficient to increase the level of alimentary fiber and the level of lipids on the 3 bread formula. The three kinds of bread that received the linseed addition and that were not irradiated presented increase on the level of total phenolic; however, when the samples which received the linseed addition were submitted to the irradiation process, it could be noticed the decrease of the antioxidant capacity. There was an increase on the level of omega-3

  12. Ionization detector

    International Nuclear Information System (INIS)

    An ionization detecting fire alarm device that comprises a double chamber structure, a source disposed in at least one of the chambers and a vernier adjusting screw electrode protruding into one chamber is described. The chamber containing the adjustable electrode is more open to the atmosphere than the other chamber, porting is provided between chambers and detection occurs by sensing the rate of change of ionization current in the chamber structure. The source or sources, one being in each chamber, is a beta source such as a nickel 63 source. A change in ionization current is detected by a unique circuit of this invention which comprises a programmable unijunction transistor oscillator circuit. 19 claims, 4 figures

  13. 超高效液相色谱-串联质谱法同时测定日化产品中的三氯生与三氯卡班%Simultaneous Determination of Triclosan and Triclocarban in Daily Chemical Products by Ultra Performance Liquid Chromatography Tandem Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    刘湘军; 赵妍; 赵珊; 杨奕; 张晶; 邱细敏; 邵兵

    2013-01-01

    采用超高效液相色谱-串联质谱技术(UPLC-MS/MS)建立了牙膏、洗手液、消毒液、洗发露、香皂等日化产品中三氯生与三氯卡班的同时分析方法.试样中的待测物经过有机溶剂超声提取,上清液稀释后,经ACQUITY UPLC HSS T3色谱柱分离,电喷雾负离子多反应检测模式(MRM)测定,外标法定量.在优化实验条件下,三氯生与三氯卡班分别在1~250、0.2~50 μg/L范围内呈良好线性(r2 >0.995),方法定量下限(LOQ)分别为0.2~0.7、0.01 ~0.02 mg/kg.3个加标水平下,三氯生与三氯卡班在5种日化产品中的加标回收率为86% ~ 116%,相对标准偏差(RSD)均不大于15%.该方法适用于日化产品中三氯生与三氯卡班的同时测定.%An ultra performance liquid chromatography - tandem mass spectrometric (UPLC - MS/ MS) method was developed for the simultaneous determination of triclosan and triclocarban in daily chemical products, including toothpaste, hand sanitizer, disinfectant, shampoo and soap. The samples were ultrasonically extracted with organic solvents and centrifugated. The analytes were separated on an ACQUITY UPLC HSS T3 column, and identified under negative electrospray ionization (ESI-) and multiple reaction monitoring(MRM) mode. The standard calibration curves were used for the quantitative analysis. Good linearities were achieved for triclosan and triclocarban over the ranges of 1 -250 μg/L and 0.2-50 μg/L, respectively, with correlation coefficients (r2) more than 0. 995. The quantitation limits of the method were in the ranges of 0. 2 -0. 7 mg/kg for triclosan and 0. 01 - 0. 02 mg/kg for triclocarban. Mean recoveries of the two target compounds in five kinds of daily chemical products at three spiked concentration levels ranged from 86% to 116% with relative standard deviations(RSDs) no more than 15% . This method could be applied in the simultaneous determination of triclosan and triclocarban in daily chemical products.

  14. Ionizing radiations

    International Nuclear Information System (INIS)

    The purpose of this article is to simplify some of the relevant points of legislation, biological effects and protection for the benefit of the occupational health nurse not familiar with the nuclear industries. The subject is dealt with under the following headings; Understanding atoms. What is meant by ionizing radiation. Types of ionizing radiation. Effects of radiation: long and short term somatic effects, genetic effects. Control of radiation: occupational exposure, women of reproductive age, medical aspects, principles of control. The occupational health nurse's role. Emergency arrangements: national arrangements for incidents involving radiation, action to be taken by the nurse. Decontamination procedures: external and internal contamination. (U.K.)

  15. Medicodosimetric register of the Siberian Group of Chemical Enterprises personnel as the basis for studying long-term effects of ionizing radiation at low doses

    International Nuclear Information System (INIS)

    On the basis of the Seversk Biophysical Research Centre (SBRC) of the Russian Federal Medical and Biological Agency there has been created a Regional Medicodosimetric Register (RMDR) of the personnel of the Siberian Group of Chemical Enterprises (SGCE) to be the world biggest complex of atomic industry enterprises. The RMDR database accumulates information of personnel, medical and dosimetric character, as well as the data on occupational activity of the workers of the main SGCE productions, namely, reactor (RP), radiochemical (RC), and plutonium (PP) ones. Information on exogenous and endogenous risk factors (RF) for main diseases development (hereditary diseases, tobacco smoking, the level of psychoemotional overload etc.) is entered into the RMDR database. To evaluate the whole spectrum of stochastic effects of ionizing radiation (IR), both 'traditional' and hypothetic ones, within RMDR there have been created such thematic registers as the register of oncologic diseases; the register of congenital malformations and hereditary diseases; the register of an acute myocardial infarction (AMI); the register of the thyroid gland diseases; the register of osteoporosis. The RMDR database includes information on almost 65,600 SGCE employees to be divided into the following cohorts: RP workers exposed to external γ-radiation (8,102 persons); RC workers with both external and internal dose loads (6,136 persons); PP workers exposed to internal radiation from incorporated 239Pu (9,434 persons). At present the share of workers of the main SGCE productions with a determined life status makes up 80%. The overwhelming majority of workers were exposed to low-dose IR (87,9% of all SGCE personnel subjected to individual dosimetric monitoring have cumulative dose of external radiation in the range 0,03-200 mSv). The RMDR structure provides for the possibility to perform analysis on both the criterion of mortality and the one of morbidity. On the basis of RMDR a large-scale spectrum

  16. Validation of a qualitative screening method for pesticides in fruits and vegetables by gas chromatography quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization

    International Nuclear Information System (INIS)

    Highlights: • Applicability of GC-(APCI)QTOF MS as new tool for wide-scope screening of pesticides in fruits and vegetables demonstrated. • Validation of screening method according to SANCO/12571/2013. • Detection of the pesticides based on the presence of M+·/MH+ in most cases. • Screening detection limit 0.01 mg kg−1 for 77% of the pesticides investigated. • Successful identification at 0.01 mg kg−1 for 70% of the pesticides/matrix combinations. - Abstract: A wide-scope screening method was developed for the detection of pesticides in fruit and vegetables. The method was based on gas chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer with an atmospheric pressure chemical ionization source (GC-(APCI)QTOF MS). A non-target acquisition was performed through two alternating scan events: one at low collision energy and another at a higher collision energy ramp (MSE). In this way, both protonated molecule and/or molecular ion together with fragment ions were obtained in a single run. Validation was performed according to SANCO/12571/2013 by analysing 20 samples (10 different commodities in duplicate), fortified with a test set of 132 pesticides at 0.01, 0.05 and 0.20 mg kg−1. For screening, the detection was based on one diagnostic ion (in most cases the protonated molecule). Overall, at the 0.01 mg kg−1 level, 89% of the 2620 fortifications made were detected. The screening detection limit for individual pesticides was 0.01 mg kg−1 for 77% of the pesticides investigated. The possibilities for identification according to the SANCO criteria, requiring two ions with a mass accuracy ≤±5 ppm and an ion-ratio deviation ≤±30%, were investigated. At the 0.01 mg kg−1 level, identification was possible for 70% of the pesticides detected during screening. This increased to 87% and 93% at the 0.05 and 0.20 mg kg−1 level, respectively. Insufficient sensitivity for the second ion was the main reason for the inability to

  17. Determination of benzoylurea insecticide residues in tomatoes by high-performance liquid chromatography with ultraviolet-diode array and atmospheric pressure chemical ionization-mass spectrometry detection.

    Science.gov (United States)

    Markoglou, Anastasios N; Bempelou, Eleftheria D; Liapis, Konstantinos S; Ziogas, Basil N

    2007-01-01

    A simple and sensitive method using high-performance liquid chromatography/ mass spectrometry (LC/MS) was developed and validated for simultaneous determination of 5 benzoylurea insecticides-diflubenzuron, triflumuron, teflubenzuron, lufenuron, and flufenoxuron-in tomatoes. Residues were successfully separated on a C18 column by methanol-water isocratic elution. Detection was carried out by an ultraviolet diode array detector (UV-DAD) coupled with a quadrupole mass spectrometer, using atmospheric pressure chemical ionization (APCI) in negative-ion mode. The main ions were the deprotonated molecules [M-H]- for triflumuron, and the anions formed by elimination of hydrofluoric acid [M-H-HF]- for diflubenzuron and flufenoxuron, and [M-2H-HF] for lufenuron and teflubenzuron. The calibration plots were linear for both detectors over the range 0.05 to 10 microg/mL, and the method presented good quality parameters. The limits of detection for standard solutions were 0.008-0.01 mg/L (equivalent to 0.08-0.1 ng injected) for both detectors, and the limits of quantification (LOQs) were approximately 10 times lower than national maximum residue levels (MRLs). Depending on the compound and the detector, the LOQ values ranged from 0.2 to 0.4 ng injected. The optimum LC-UV-DAD/APCI-MS conditions were applied to the analysis of benzoylureas in tomatoes. The obtained recoveries from fortified tomato samples (50 g), extracted with ethyl acetate and purified by solid-phase extraction on silica sorbent, were 88-100 and 92.9-105% for the UV-DAD and MS detectors, respectively, with precision values (relative standard deviations) of 2.9-11 and 3.7-14%, respectively. The method was applied to 12 tomato samples from local markets, and diflubenzuron and lufenuron were detected in only one sample at concentrations lower than the MRLs. The results indicate that the developed LC/MS method is accurate, precise, and sensitive for quantitative and qualitative analysis at low levels of benzoylureas

  18. Validation of a qualitative screening method for pesticides in fruits and vegetables by gas chromatography quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization

    Energy Technology Data Exchange (ETDEWEB)

    Portolés, T. [Research Institute for Pesticides and Water, University Jaume I, 12071 Castellón (Spain); RIKILT Institute of Food Safety, Wageningen University and Research Centre, Akkermaalsbos 2, 6708 WB Wageningen (Netherlands); Mol, J.G.J. [RIKILT Institute of Food Safety, Wageningen University and Research Centre, Akkermaalsbos 2, 6708 WB Wageningen (Netherlands); Sancho, J.V.; López, Francisco J. [Research Institute for Pesticides and Water, University Jaume I, 12071 Castellón (Spain); Hernández, F., E-mail: hernandf@uji.es [Research Institute for Pesticides and Water, University Jaume I, 12071 Castellón (Spain)

    2014-08-01

    Highlights: • Applicability of GC-(APCI)QTOF MS as new tool for wide-scope screening of pesticides in fruits and vegetables demonstrated. • Validation of screening method according to SANCO/12571/2013. • Detection of the pesticides based on the presence of M+·/MH+ in most cases. • Screening detection limit 0.01 mg kg{sup −1} for 77% of the pesticides investigated. • Successful identification at 0.01 mg kg{sup −1} for 70% of the pesticides/matrix combinations. - Abstract: A wide-scope screening method was developed for the detection of pesticides in fruit and vegetables. The method was based on gas chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer with an atmospheric pressure chemical ionization source (GC-(APCI)QTOF MS). A non-target acquisition was performed through two alternating scan events: one at low collision energy and another at a higher collision energy ramp (MS{sup E}). In this way, both protonated molecule and/or molecular ion together with fragment ions were obtained in a single run. Validation was performed according to SANCO/12571/2013 by analysing 20 samples (10 different commodities in duplicate), fortified with a test set of 132 pesticides at 0.01, 0.05 and 0.20 mg kg{sup −1}. For screening, the detection was based on one diagnostic ion (in most cases the protonated molecule). Overall, at the 0.01 mg kg{sup −1} level, 89% of the 2620 fortifications made were detected. The screening detection limit for individual pesticides was 0.01 mg kg{sup −1} for 77% of the pesticides investigated. The possibilities for identification according to the SANCO criteria, requiring two ions with a mass accuracy ≤±5 ppm and an ion-ratio deviation ≤±30%, were investigated. At the 0.01 mg kg{sup −1} level, identification was possible for 70% of the pesticides detected during screening. This increased to 87% and 93% at the 0.05 and 0.20 mg kg{sup −1} level, respectively. Insufficient sensitivity for the second

  19. Measurements of HNO3 and N2O5 using ion drift-chemical ionization mass spectrometry during the MILAGRO/MCMA-2006 campaign

    Directory of Open Access Journals (Sweden)

    X. Tie

    2008-11-01

    Full Text Available An ion drift-chemical ionization mass spectrometer (ID-CIMS was deployed in Mexico City between 7 and 31 March to measure gas-phase nitric acid (HNO3 and dinitrogen pentoxide (N2O5 during the Mexico City Metropolitan Area (MCMA-2006 field campaign. The observation site was located at the Instituto Mexicano del Petróleo in the northern part of Mexico City urban area with major emissions of pollutants from residential, vehicular and industrial sources. Diurnally, HNO3 was less than 200 parts per trillion (ppt during the night and early morning. The concentration of HNO3 increased steadily from around 09:00 a.m. central standard time (CST, reached a peak value of 0.5 to 3 parts per billion (ppb in the early afternoon, and then declined sharply to less than half of the peak value near 05:00 p.m. CST. An inter-comparison between the ID-CIMS and an ion chromatograph/mass spectrometer (ICMS showed a good agreement between the two HNO3 measurements (R2=0.75. The HNO3 mixing ratio was found to anti-correlate with submicron-sized aerosol nitrate, suggesting that the gas-particle partitioning process was a major factor in determining the gaseous HNO3 concentration. Losses by irreversible reactions with mineral dust and via dry deposition also could be important at this site. Most of the times during the MCMA 2006 field campaign, N2O5 was found to be below the detection limit (about 30 ppt for a 10 s integration time of the ID-CIMS, because of high NO mixing ratio at the surface (>100 ppb during the night. An exception occurred on 26 March 2006, when about 40 ppt N2O5 was observed during the late afternoon and early evening hours under cloudy conditions before the build-up of NO at the surface site. The results revealed that during the MCMA-2006 field campaign HNO3 was primarily produced from the reaction of OH with NO2 and regulated by gas/particle transfer and dry deposition. The production of HNO3 from N2O5 hydrolysis during the nighttime was small

  20. Measurements of HNO3 and N2O5 using ion drift-chemical ionization mass spectrometry during the MILAGRO/MCMA-2006 campaign

    Science.gov (United States)

    Zheng, J.; Zhang, R.; Fortner, E. C.; Volkamer, R. M.; Molina, L.; Aiken, A. C.; Jimenez, J. L.; Gaeggeler, K.; Dommen, J.; Dusanter, S.; Stevens, P. S.; Tie, X.

    2008-11-01

    An ion drift-chemical ionization mass spectrometer (ID-CIMS) was deployed in Mexico City between 7 and 31 March to measure gas-phase nitric acid (HNO3) and dinitrogen pentoxide (N2O5 during the Mexico City Metropolitan Area (MCMA)-2006 field campaign. The observation site was located at the Instituto Mexicano del Petróleo in the northern part of Mexico City urban area with major emissions of pollutants from residential, vehicular and industrial sources. Diurnally, HNO3 was less than 200 parts per trillion (ppt) during the night and early morning. The concentration of HNO3 increased steadily from around 09:00 a.m. central standard time (CST), reached a peak value of 0.5 to 3 parts per billion (ppb) in the early afternoon, and then declined sharply to less than half of the peak value near 05:00 p.m. CST. An inter-comparison between the ID-CIMS and an ion chromatograph/mass spectrometer (ICMS) showed a good agreement between the two HNO3 measurements (R2=0.75). The HNO3 mixing ratio was found to anti-correlate with submicron-sized aerosol nitrate, suggesting that the gas-particle partitioning process was a major factor in determining the gaseous HNO3 concentration. Losses by irreversible reactions with mineral dust and via dry deposition also could be important at this site. Most of the times during the MCMA 2006 field campaign, N2O5 was found to be below the detection limit (about 30 ppt for a 10 s integration time) of the ID-CIMS, because of high NO mixing ratio at the surface (>100 ppb) during the night. An exception occurred on 26 March 2006, when about 40 ppt N2O5 was observed during the late afternoon and early evening hours under cloudy conditions before the build-up of NO at the surface site. The results revealed that during the MCMA-2006 field campaign HNO3 was primarily produced from the reaction of OH with NO2 and regulated by gas/particle transfer and dry deposition. The production of HNO3 from N2O5 hydrolysis during the nighttime was small because of

  1. III. Penning ionization, associative ionization and chemi-ionization processes

    International Nuclear Information System (INIS)

    Physical mechanisms of three important ionization processes in a cold plasma and the methods of their experimental study are discussed. An apparatus for the investigation of the Penning ionization using ionization processes of long lived metastable rare gas atoms is described. Methods of determining interaction energies and ionization rates from the measured energy spectra of the originating electrons are described and illustrated by several examples. Typical associative ionization processes are listed and the ionization rates are compared with those of the Penning ionization. Interactions with short-lived excited particles and the transfer of excitation without ionization are discussed. (J.U.)

  2. 10 years Rossendorf Tandem

    International Nuclear Information System (INIS)

    10 years successful operation of the Rossendorf Tandem is an occasion to give an account about the most important developments and results in the fields of accelerator technology and utilization of this machine. The selected and sum up contributions reflect the systematic orientation on increasing the availability of the accelerator as well as its improvement to an effective heavy ion accelerator to extend the quantitative and qualitative possibilities of application in nuclear physical experiments. (author)

  3. Tandem physics in Orsay

    International Nuclear Information System (INIS)

    An account is given of the very good and reliable running of the Orsay MP tandem accelerator at 13MeV. The experimental equipment is briefly described and a summary of the scientific program is given, illustrated by a few chosen examples in each main domain of research: spectroscopy by transfer reactions, angular correlations and γ-desexcitation, mechanisms of the scattering in symmetrical systems and polarization in heavy ions reactions, studies of exotic nuclei

  4. Ionizing radiation

    International Nuclear Information System (INIS)

    The subject is discussed under the headings: characteristics of ionizing radiations; biological effects; comparison of radiation and other industrial risks; principles of protection; cost-benefit analysis; dose limits; the control and monitoring of radiation; reference levels; emergency reference levels. (U.K.)

  5. Microcrystalline silicon and the impact on micromorph tandem solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Meier, J.; Dubail, S.; Golay, S.; Kroll, U.; Fay, E.; Vallat-Sauvain, E.; Feitknecht, L.; Dubail, J.; Shah, A. [Universite de Neuchatel (Switzerland). Inst. de Microtechnique

    2002-10-01

    Intrinsic microcrystalline silicon opens up new ways for silicon thin-film multi-junction solar cells, the most promising being the 'micromorph' tandem concept. The microstructure of entirely microcrystalline p-i-n solar cells is investigated by transmission electron microscopy. By applying low pressure chemical vapor deposition ZnO as front TCO in p-i-n configurated micromorph tandems, a remarkable reduction of the microcrystalline bottom cell thickness is achieved. Micromorph tandem cells with high open circuit voltages of 1.413 V could be accomplished. A stabilized efficiency of around 11% is estimated for micromorph tandems consisting of 2 {sup {mu}}m thick bottom cells. Applying the monolithic series connection, a micromorph module (23.3 cm{sup 2}) of 9.1% stabilized efficiency could be obtained. (Author)

  6. 超高效液相色谱-电喷雾串联质谱法测定塑料成品中的三甲基氯化锡%Determination of trimethyltin in plastic product by using ultra high performance liquid chromatography electrospray ionization tandem mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    陈慧玲; 许欣欣; 毛丽莎; 刘红河; 陆少游

    2016-01-01

    目的:建立塑料成品中三甲基氯化锡(TMT)的超高效液相色谱-串联质谱联用测定法(UPLC-MS/MS)。方法塑料样品用乙酸乙酯提取,洗脱液在40℃水浴下氮气吹干;残渣用流动相溶解,旋涡混匀60s,过0.22μm微孔滤膜,经C18色谱柱完成分离,串联质谱仪上采用多反应监测正离子模式测定三甲基氯化锡,外标法定量。结果三甲基氯化锡在1.0~100.0μg/L 范围内线性关系良好(相关系数 r=0.9997),检出限0.2μg/L。在2.0、10.0和50.0μg/L 3个添加水平范围的RSD小于8.0%,样品加标回收率为88.5%~93.4%。结论建立的超高效液相色谱-串联质谱联用法测定塑料成品中三甲基氯化锡的方法快速简单、准确有效。%Objective An ultra-high performance liquid chromatography eclectrospray ionization tandem mass spectrometry (UPLC-MS/MS) method was developed to determine trimethyltin (TMT) in plastic product. Methods TMT was extracted from plastic product by ethyl acetate, the elute was evaporated to dryness with nitrogen in 40℃ water bath, redissolved with 1ml of moble phase solution, vortexed for 60 s and filtered with 0.22 μm membrane. The filtrate was detected by UPLC-MS/MS in positive ion electrospray and MRM mode with a UPLC C18 column as separation column, and quantified with external standard substances. Results TMT was linear in the range of 1.0~100.0 μg/L with correlation coefficient of 0.9997. The relative standard derivations (RSD) at three levels (2.0 μg/L、10.0 μg/L and 50.0 μg/L) were lower than 8.0%, and the recovery rate was from 88.5% to 93.4%. Conclusion The method of liquid chromatography-electrospray tandem mass spectrometry is simple, reliable and accurate, that adapts to determinate TMT in plastic product.

  7. CHEMICALS

    CERN Multimedia

    Medical Service

    2002-01-01

    It is reminded that all persons who use chemicals must inform CERN's Chemistry Service (TIS-GS-GC) and the CERN Medical Service (TIS-ME). Information concerning their toxicity or other hazards as well as the necessary individual and collective protection measures will be provided by these two services. Users must be in possession of a material safety data sheet (MSDS) for each chemical used. These can be obtained by one of several means : the manufacturer of the chemical (legally obliged to supply an MSDS for each chemical delivered) ; CERN's Chemistry Service of the General Safety Group of TIS ; for chemicals and gases available in the CERN Stores the MSDS has been made available via EDH either in pdf format or else via a link to the supplier's web site. Training courses in chemical safety are available for registration via HR-TD. CERN Medical Service : TIS-ME :73186 or service.medical@cern.ch Chemistry Service : TIS-GS-GC : 78546

  8. Desorption electrospray ionization of explosives on surfaces: sensitivity and selectivity enhancement by reactive desorption electrospray ionization.

    Science.gov (United States)

    Cotte-Rodríguez, Ismael; Takáts, Zoltán; Talaty, Nari; Chen, Huanwen; Cooks, R Graham

    2005-11-01

    Desorption electrospray ionization (DESI), an ambient mass spectrometry technique, is used for trace detection of the explosives trinitrohexahydro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 2,4,6-trinitrotoluene (TNT), Pentaerythritol tetranitrate (PETN), and their plastic compositions (Composition C-4, Semtex-H, Detasheet) directly from a wide variety of surfaces (metal, plastic, paper, polymer) without sample preparation or pretreatment. Analysis of the explosives is performed under ambient conditions from virtually any surface in very short times (<5 s) including confirmatory tandem mass spectrometry (MS/MS) experiments, while retaining the sensitivity and specificity that mass spectrometry offers. Increased selectivity is obtained both by MS/MS and by performing additional experiments in which additives are included in the spray solvent. These reactive DESI experiments (reactions accompanying desorption) produce such ions as the chloride and trifluoroacetate adducts of RDX and HMX or the Meisenheimer complex of TNT. Desorption atmospheric pressure chemical ionization, a variant of DESI that uses gas-phase ions generated by atmospheric pressure corona discharges of toluene or other organic compounds, provides evidence for a heterogeneous-phase (gaseous ion/absorbed analyte) charge-transfer mechanism of DESI ionization in the case of explosives. Plastic explosives on surfaces were analyzed directly as fingerprints, without sample preparation, to test DESI as a possible method for in situ detection of explosives-contaminated surfaces. DESI also allowed detection of explosives in complex matrixes, including lubricants, household cleaners, vinegar, and diesel fuel. Absolute limits of detection for the neat explosives were subnanogram in all cases and subpicogram in the case of TNT. The DESI response was linear over 3 orders of magnitude for TNT. Quantification of RDX on paper gave a precision (RSD) of 2.3%. Pure water could be used

  9. Automated mini-column solid-phase extraction cleanup for high-throughput analysis of chemical contaminants in foods by low-pressure gas chromatography – tandem mass spectrometry

    Science.gov (United States)

    This study demonstrated the application of an automated high-throughput mini-cartridge solid-phase extraction (mini-SPE) cleanup for the rapid low-pressure gas chromatography – tandem mass spectrometry (LPGC-MS/MS) analysis of pesticides and environmental contaminants in QuEChERS extracts of foods. ...

  10. Effects of ionizing radiation in the physico-chemical characteristics of red wine Cabernet Sauvignon; Efeitos da radiacao ionizante nas caracteristicas fisico-quimicas do vinho tinto Cabernet Sauvignon

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Fellipe Souza da; Leiras, Anderson; Wagner, Walsan, E-mail: fellipe.souzadasilva@gmail.com [Instituto de Radioprotecao e Dosimetria, (IRD/CNEN-RJ), Rio de Janeiro, RJ (Brazil)

    2014-07-01

    The oenology in the current days is increasingly aimed obtain improvements on wine quality produced without there the deterioration of characteristics of the same, using new technologies for such order. The objective of present work will be the application of the radiation ionizing in wines Cabernet Sauvignon, with the interest of analyzing its effects on physic-chemical characteristics of this wines, such as quality, aging and etc. Were analyzed the following strands: degree alcoholic; dry extract; density and absorbance with spectrometer (420, 520 and 620 nm). (author)

  11. Bifacial tandem solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Wojtczuk, Steven J.; Chiu, Philip T.; Zhang, Xuebing; Gagnon, Edward; Timmons, Michael

    2016-06-14

    A method of fabricating on a semiconductor substrate bifacial tandem solar cells with semiconductor subcells having a lower bandgap than the substrate bandgap on one side of the substrate and with subcells having a higher bandgap than the substrate on the other including, first, growing a lower bandgap subcell on one substrate side that uses only the same periodic table group V material in the dislocation-reducing grading layers and bottom subcells as is present in the substrate and after the initial growth is complete and then flipping the substrate and growing the higher bandgap subcells on the opposite substrate side which can be of different group V material.

  12. Negative tandem mirror

    International Nuclear Information System (INIS)

    A tandem mirror configuration can be created by combining hot electron end cell plasmas with neutral beam pumping. A region of large negative potential formed in each end cell confines electrons in the central cell. The requirement of charge neutrality causes the central cell potential to become negative with respect to ground in order to confine ions as well as electrons. We discuss the method of producing and calculating the desired axial potential profile, and show the calculated axial potential profile and plasma parameters for a negative configuration of TMX-Upgrade

  13. Comparative analysis of sweat patches for cocaine (and metabolites) by radioimmunoassay and gas chromatography-positive ion chemical ionization-mass spectrometry.

    Science.gov (United States)

    Moody, David E; Spanbauer, Alan C; Taccogno, James L; Smith, Elizabeth K

    2004-03-01

    Immunoassays are commonly used to screen samples prior to confirmation by gas chromatography-mass spectrometry (GC-MS). This serves two purposes: it provides a second method for positive samples, and it allows exclusion of negative samples from further confirmatory testing. In addition, immunoassay results can be used in some cases to determine if dilution of the sample will be required during the confirmatory assay. We used 878 sweat patches worn by 38 subjects receiving treatment for cocaine dependence to compare analysis of the extracts of the patches for cocaine immuno-equivalents by radioimmunoassay (RIA) with determination of cocaine, benzoylecgonine (BE), and ecgonine methyl ester (EME) by GC-MS. Preliminary validation experiments demonstrate that the GC-MS method using positive ion chemical ionization had sufficient specificity and recovery to support a lower limit of quantitation (LLOQ) of 4 ng/patch and was precise and accurate across a linear range up to 500 ng/patch. Cocaine ranging from the LLOQ to 31,900 ng/patch was found in 660 of the samples; BE ranging from the LLOQ to 3470 ng/patch was found in 530 of the samples; and EME ranging from the LLOQ to 2280 ng/patch was found in 476 of the samples. In a subset of 238 samples semiquantitative use of the RIA gave results that agreed with GC-MS with a correlation coefficient of 0.986, but averaged approximately 23% lower. Although this accuracy of the RIA supported its use as a sole quantitative assay, the limited linear range of the RIA (4-200 ng/patch) proved impractical for this purpose. Receiver operator characteristic analysis of the cutoffs of the RIA and GC-MS suggested optimal cutoffs of 5 and 4 ng/patch, respectively. At these cutoffs, the RIA had sensitivity of 90.0% and specificity of 92.2%. For samples that had RIA results greater than the high calibrator (N = 228), various dilution schemes were assessed for their ability to predict retention of either cocaine alone or cocaine and both

  14. A multi-residue method for pesticides analysis in green coffee beans using gas chromatography-negative chemical ionization mass spectrometry in selective ion monitoring mode.

    Science.gov (United States)

    Pizzutti, Ionara R; de Kok, Andre; Dickow Cardoso, Carmem; Reichert, Bárbara; de Kroon, Marijke; Wind, Wouter; Weber Righi, Laís; Caiel da Silva, Rosselei

    2012-08-17

    In this study, a new gas chromatography-mass spectrometry (GC-MS) method, using the very selective negative chemical ionization (NCI) mode, was developed and applied in combination with a modified acetonitrile-based extraction method (QuEChERS) for the analysis of a large number of pesticide residues (51 pesticides, including isomers and degradation products) in green coffee beans. A previously developed integrated sample homogenization and extraction method for both pesticides and mycotoxins analysis was used. An homogeneous slurry of green milled coffee beans and water (ratio 1:4, w/w) was prepared and extracted with acetonitrile/acetic acid (1%), followed by magnesium sulfate addition for phase separation. Aliquots from this extract could be used directly for LC-MS/MS analysis of mycotoxins and LC-amenable pesticides. For GC-MS analysis, a further clean-up was necessary. C18- and PSA-bonded silica were tested as dispersive solid-phase extraction (d-SPE) sorbents, separate and as a mixture, and the best results were obtained using C18-bonded silica. For the optimal sensitivity and selectivity, GC-MS detection in the NCI-selected ion monitoring (SIM) mode had to be used to allow the fast analysis of the difficult coffee bean matrix. The validation was performed by analyzing recovery samples at three different spike concentrations, 10, 20 and 50 μg kg(-1), with 6 replicates (n=6) at each concentration. Linearity (r(2)) of calibration curves, estimated instrument and method limits of detection and limits of quantification (LOD(i), LOD(m), LOQ(i) and LOQ(m), respectively), accuracy (as recovery %), precision (as RSD%) and matrix effects (%) were determined for each individual pesticide. From the 51 analytes (42 parent pesticides, 4 isomers and 5 degradation products) determined by GC-MS (NCI-SIM), approximately 76% showed average recoveries between 70-120% and 75% and RSD ≤ 20% at the lowest spike concentration of 10 μg kg(-1), the target method LOQ. For the

  15. Novel two-step laser ablation and ionization mass spectrometry (2S-LAIMS) of actor-spectator ice layers: Probing chemical composition of D2O ice beneath a H2O ice layer

    International Nuclear Information System (INIS)

    In this work, we report for the first time successful analysis of organic aromatic analytes imbedded in D2O ices by novel infrared (IR) laser ablation of a layered non-absorbing D2O ice (spectator) containing the analytes and an ablation-active IR-absorbing H2O ice layer (actor) without the analyte. With these studies we have opened up a new method for the in situ analysis of solids containing analytes when covered with an IR laser-absorbing layer that can be resonantly ablated. This soft ejection method takes advantage of the tenability of two-step infrared laser ablation and ultraviolet laser ionization mass spectrometry, previously demonstrated in this lab to study chemical reactions of polycyclic aromatic hydrocarbons (PAHs) in cryogenic ices. The IR laser pulse tuned to resonantly excite only the upper H2O ice layer (actor) generates a shockwave upon impact. This shockwave penetrates the lower analyte-containing D2O ice layer (spectator, a non-absorbing ice that cannot be ablated directly with the wavelength of the IR laser employed) and is reflected back, ejecting the contents of the D2O layer into the vacuum where they are intersected by a UV laser for ionization and detection by a time-of-flight mass spectrometer. Thus, energy is transmitted from the laser-absorbing actor layer into the non-absorbing spectator layer resulting its ablation. We found that isotope cross-contamination between layers was negligible. We also did not see any evidence for thermal or collisional chemistry of PAH molecules with H2O molecules in the shockwave. We call this “shockwave mediated surface resonance enhanced subsurface ablation” technique as “two-step laser ablation and ionization mass spectrometry of actor-spectator ice layers.” This method has its roots in the well-established MALDI (matrix assisted laser desorption and ionization) method. Our method offers more flexibility to optimize both the processes—ablation and ionization. This new technique can thus be

  16. Modification of the Argonne tandem

    International Nuclear Information System (INIS)

    For nuclear structure experiments with heavy ions it is necessary to have ion energies in excess of 5 MeV per nucleon. At the Argonne tandem FN accelerator this was accomplished by the addition of a superconducting linac. Modifications of the FN tandem to improve the performance of the pair is described

  17. Quantum-chemical calculations of the products and energies of electron induced ionization of 2-Furanmethanol, Tetrahydro-and 3-Furanol

    Directory of Open Access Journals (Sweden)

    Papp P.

    2008-01-01

    Full Text Available A theoretical treatment is used to perform conformational studies of title compounds, which was previously successfully used within our group for characterization of fragmentation patterns of some bio-molecules. Now we present studies of electron impact ionization of 2 Furanmethanol, Tetrahydro (C5H10O2 and 3-Furanol, Tetrahydro (C4H8O2, both as important models for more complicated compounds like nucleic acids. In this paper geometry of the neutral and cationic conformers of these two molecules was optimized on the DFT level with B3LYP functional, and ionization energies were estimated. DFT calculated results are supplemented with G3MP2 calculations, and a set of higher-level ab initio methods were empirically corrected to obtain more reliable results.

  18. Chemical analysis of surfaces by resonance ionization mass spectroscopy associated to ionic pulverization; Analyse chimique de surfaces par spectrometrie d`ionisation resonante associee a la pulverisation ionique

    Energy Technology Data Exchange (ETDEWEB)

    Kern, P.

    1995-12-19

    This work shows that if resonance ionization mass spectroscopy was first applied in isotopic separation, it`s also an analyzing method adapted to the study of semi-conductor materials and thin foils. We have improved this technic: a neodymium laser coupled with a dye laser, a new argon ions gun, a gallium ions gun and a new collection optic for the secondary ions quadrupole spectrometer to allow quantitative and selective measurements. (S.G.). 84 refs.

  19. JAERI tandem-accelerator and tandem-booster

    Energy Technology Data Exchange (ETDEWEB)

    Yoshida, Tadashi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1998-03-01

    In 1982, aiming at the new development of atomic energy research, the tandem accelerator of Japan Atomic Energy Research Institute (JAERI) was installed. In fiscal year 1993, the superconducting boosters which can increase the ion energy by up to 4 times were added, and the research in the region below 1000 MeV became possible. Those are electrostatic type accelerators which are easy to be used especially in basic research field, and are useful for future research. The tandem accelerator has been operated while maintaining the first class performance as the accelerator for various kinds of heavy ion beam. It has the special shape among electrostatic type accelerators, and is excellent in the easiness of control and stability. The main particulars of the tandem accelerator are shown. As for the ion sources of the tandem accelerator, three cesium sputter type ion sources are installed on two high voltage stands. The kinds of the ions which can be accelerated are mainly negative ions. As the improvement, electron cyclotron resonance (ECR) ion sources are expected to be adopted. As for the tandem boosters, the 1/4 wavelength type resonance hollow cylinder was adopted. The constitution of the tandem boosters is explained. The way of utilizing the tandem accelerator system and the aim for hereafter are reported. (K.I.)

  20. Ionization chamber

    International Nuclear Information System (INIS)

    An ionization chamber X-ray detector is described. It comprises a flat cathode sheet parallel to an anode which has a perforated insulating layer on its surface. An open grid, a thin perforated metal sheet is disposed on the insulating layer - the perforations of the layer and sheet are aligned. There is a detector gas and means for maintaining the grid at an electric potential between that of the anode and cathode and for measuring the current flow from the anode to the cathode. The grid shields the anode from the electric field produced by the positive ions which flow towards the cathode and this permits an independent measurement of the electron current flowing to the anode; even when the X-ray pulse length is not much shorter than the ion drift time. The recovery time of the ionization chamber is thus decreased by several orders of magnitude over previous chambers. The grid will normally be fixed to the anode and by shielding the anode from the cathode electric field, tends to eliminate capacitive microphone currents which would otherwise flow in the anode circuit. (U.K.)

  1. Production of Ar{sup q+} ions with a tandem linear Paul trap

    Energy Technology Data Exchange (ETDEWEB)

    Higaki, H., E-mail: hhigaki@hiroshima-u.ac.jp; Nagayasu, K.; Iwai, T.; Ito, K.; Okamoto, H. [Graduate School of Advanced Sciences of Matter, Hiroshima University 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8530 Japan (Japan)

    2015-06-29

    A tandem linear Paul trap was used to create highly charged Argon ions by electron impact ionizations. By improving the operation scheme, the production of Ar{sup 4+} ions was confirmed. Possible improvements for the future experiments with laser cooled Ca{sup +} ions are suggested.

  2. Resonance ionization spectroscopy

    International Nuclear Information System (INIS)

    The subject of resonance ionization spectroscopy (RIS) from its inception to the present is summarized. The uses of RIS are principally analytical, and these uses are classified in several different ways for this report. The classifications are: (1) basic ways of counting atoms; (2) RIS applications according to the type of particle detector; (3) applications according to source preparation; (4) applications in chemical physics and chemistry; and (5) applications involving daughter atom detection. Each classification is discussed in some detail, and examples of specific applications are mentioned under each classification. Some other potential applications not necessarily related to these classifications are also mentioned

  3. Synfuels from fusion: producing hydrogen with the Tandem Mirror Reactor and thermochemical cycles

    International Nuclear Information System (INIS)

    This volume contains the following sections: (1) the Tandem Mirror fusion driver, (2) the Cauldron blanket module, (3) the flowing microsphere, (4) coupling the reactor to the process, (5) the thermochemical cycles, and (6) chemical reactors and process units

  4. Synfuels from fusion: producing hydrogen with the Tandem Mirror Reactor and thermochemical cycles

    Energy Technology Data Exchange (ETDEWEB)

    Werner, R.W.; Ribe, F.L.

    1981-01-21

    This volume contains the following sections: (1) the Tandem Mirror fusion driver, (2) the Cauldron blanket module, (3) the flowing microsphere, (4) coupling the reactor to the process, (5) the thermochemical cycles, and (6) chemical reactors and process units. (MOW)

  5. Fueling of tandem mirror reactors

    International Nuclear Information System (INIS)

    This paper summarizes the fueling requirements for experimental and demonstration tandem mirror reactors (TMRs), reviews the status of conventional pellet injectors, and identifies some candidate accelerators that may be needed for fueling tandem mirror reactors. Characteristics and limitations of three types of accelerators are described; neutral beam injectors, electromagnetic rail guns, and laser beam drivers. Based on these characteristics and limitations, a computer module was developed for the Tandem Mirror Reactor Systems Code (TMRSC) to select the pellet injector/accelerator combination which most nearly satisfies the fueling requirements for a given machine design

  6. Dosimetry of ionizing radiation

    International Nuclear Information System (INIS)

    The book informs of the whole range of the physical foundations of dosimetry. In the chapter dealing with the interaction of ionizing radiation with matter the processes are described of the interaction between the individual types of ionizing radiation and matter and the effects of ionizing radiation on matter. The chapter dealing with dosimetric quantities and units gives a survey and definitions of quantities and their inter-relations. The chapters relating to the determination of basic dosimetric quantities and to integral dosimetric methods give a detailed description of the individual methods. The chapter relating to radionuclides in the environment concerns the occurrence of natural radionuclides in the environment and in the human organism, cosmic radiation and artificial sources of radioactivity connected with the development of civilisation and technology. The chapter related to radiation protection gives guidelines for the calculation of shielding for individual types of radiation. The supplement contains a list of the properties of certain radionuclides widespread in the environment, their basic physico-chemical and biological characteristics, parameters of metabolism and values of maximum permissible concentrations. (M.D.)

  7. Sensitive liquid chromatography-tandem mass spectrometry method for the simultaneous determination of paracetamol and guaifenesin in human plasma.

    Science.gov (United States)

    Chen, Xiaoyan; Huang, Jia; Kong, Zhang; Zhong, Dafang

    2005-03-25

    A rapid and sensitive method for the simultaneous determination of paracetamol and guaifenesin in human plasma was developed and validated, using high-performance liquid chromatographic separation with tandem mass spectrometric detection. After extracted from plasma samples by diethyl ether-dichloromethane (3:2, v/v), the analytes and internal standard osalmide were chromatographed on a C18 column. Detection was performed on a triple quadrupole tandem mass spectrometer by selected reaction monitoring (SRM) mode via atmospheric pressure chemical ionization (APCI). The method was linear in the concentration range of 0.05-20.0 microg/ml for paracetamol and 5.0-2000.0 ng/ml for guaifenesin. The intra- and inter-day precision was within 14% for both paracetamol and guaifenesin. The assay accuracy was within +/-2.4% for the analytes. This is the first assay method described for the simultaneous determination of paracetamol and guaifenesin in plasma using one chromatographic run. The method was successfully employed in a pharmacokinetic study after an oral administration of a multicomponent formulation, containing 650 mg paracetamol, 200 mg guaifenesin, 60 mg pseudoephedrine and 20 mg dextrorphan. PMID:15686994

  8. Biopositive Effects of Ionizing Radiation?

    International Nuclear Information System (INIS)

    This paper was written for a talk given by E. Broda in Vienna for an event organised by the chemical physical society, the Austrian biochemical society and the Austrian biophysical society in December 1972. In this paper Broda analyses the question of biopositive effects of ionizing radiation. (nowak)

  9. METHOD 521: DETERMINATION OF NITROSAMINES IN DRINKING WATER BY SOLID PHASE EXTRACTION AND CAPILLARY COLUMN GAS CHROMATOGRAPHY WITH LARGE VOLUME INJECTION AND CHEMICAL IONIZATION TANDEM MASS SPECTROMETRY (MS/MS)

    Science.gov (United States)

    NDMA is an emerging drinking water contaminant that is of interest to EPA and the environmental community. Its presence in drinking water is a potential health concern, because the EPA's IRIS data base lists the concentration of NDMA required to result in a one in one million li...

  10. 纺织品中致癌性芳香胺的质谱成像%Imaging Carcinogenic Aromatic Amines in Textiles by Surface Desorption Atmospheric Pressure Chemical Ionization Tandem Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    丁丽英; 胡斌; 杨水平; 李建强; 陈焕文

    2010-01-01

    表面解析常压化学电离串联质谱(SDAPCI-MS~n)可以在无需样品预处理的条件下直接检测纺织品中存在的致癌性邻甲苯胺.在此基础上,分别以质子化邻甲苯胺(m/z 108)及其特征峰碎片离子(m/z 91)为探针,对穿过的衣服袖口进行二维质谱扫描,用不同颜色表示袖口上芳香胺信号强度的高低,在无损衣服的情况下获得该袖口上邻甲苯胺的质谱影像,从分子层次上对衣袖中邻甲苯胺的分布进行可视化表达,所成像图的空间分辨率达0.2 mm~2,对了解致癌性芳香胺在纺织品中的分布具有重要意义.

  11. Ionization gage

    International Nuclear Information System (INIS)

    An ionization manometer is proposed which contains a transducer consisting of an anode, a directly heated cathode and a collector, a power source, a cathode emission current stabilizer, an ionic current amplifier connected to a recorder, and a cathode emission current modulator. To increase the accuracy of measurements under conditions of vacuum evaporation of materials, the modulator has been designed to comprise a source of controlling electric unipolar pulses of a specified duration and frequency and a blocking device connected to the collector. The output of the source of controlling electric unipolar pulses is connected to the emission current stabilizer and to the second input of the blocking device whose output is connected to the ionic current amplifier. The amount of pressure exerted in the vacuum chamber is estimated from the magnitude of the variable constituent of the collector signal

  12. 玉米中9种磺酰脲类除草剂的超高效液相色谱-串联质谱法同时测定%Simultaneous Determination of 9 Sulfonylurea Herbicides in Corn Using Solid-phase Extraction and Ultra Performance Liquid Chromatography with Electrospray Ionization Tandem Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    丁菲; 李范珠; 储晓刚; 张峰; 凌云; 孙利; 杨敏莉; 吕泉福; 许成保

    2011-01-01

    采用超高效液相色谱-串联四极杆质谱(UPLC-MS/MS),在多反应监测(MRM )模式下建立了玉米中9种磺酰脲类除草剂残留的定性定量分析方法.样品浸泡后采用甲醇-丙酮(体积比1:1)提取、浓缩,经C18固相萃取柱净化处理.采用UPLC-ESI MS/MS方法测定,外标法定量.9种磺酰脲类除草剂在0.05~2.0 mg·L-1范围内具有较好的线性关系,相关系数均大于0.99,该方法的检出限(LOD,S/N=3)为0.001~0.005 mg·L-1,定量下限(LOQ,S/N=10)为0.062~0.080 mg·kg-1.在1LOQ、2LOQ和5LOQ 3个加标水平下的回收率为60%~85%,相对标准偏差(RSDs)均在10%以内.该方法简便快速,满足玉米中9种磺酰脲类除草剂的快速检测要求.%A new method based on solid phase extraction and ultra performance liquid chromatography -tandem mass spectrometry( UPLC -ESI MS/MS) was developed for the determination of 9 sulfonylurea herbicides(metoxuron, foramsulfuron, cinosulfuron, methabenthiazuron, prosulfuron, linuron, ethoxysulfuron, chloroxuron and cyclosulfamuron) in corn. The corn sample was soared in water, and then extracted with methanol - acetone ( 1: 1, by volume). The extract was cleaned up by C18 solid phase extraction cartridge. The eluent was evaporated to near dryness under a stream of nitregen gas, and redissolved by methanol. The identification and detection of target compounds were achieved under multiple reactions monitoring (MRM) mode with positive electrospray ionization (ESI). 9 sulfonylurea herbcides were quantified by external standard method. The calibration curves of 9 sulfonylurea herbicides were linear in the range of 0. 05 - 2.0 mg · L-1 with correlation coefficients more than O. 99. The limits of detection ( LOD, S/N = 3 ) and the limits of quantitation ( LOQ, S/N= 10) were in the range of 0. 001 -0. 005 mg · L-1 and 0. 062 -0. 080 mg · kg-1, respectively. 1LOQ,2LOQ and 5LOQ were chosen as the three spiked levels of recovery for the method. The recoveries of 9

  13. A Supercritical Fluid Chromatography/Tandem Mass Spectrometry Method for the Simultaneous Quantification of Metformin and Gliclazide in Human Plasma

    OpenAIRE

    Agrawal Y; Gogoi P; Manna K; Bhatt H; Jain V

    2010-01-01

    Present study reports the development and validation of a simultaneous estimation of metformin and gliclazide in human plasma using supercritical fluid chromatography followed by tandem mass spectrometry. Acetonitrile:water (80:20) mixture was used as a mobile phase along with liquid CO 2 in supercritical fluid chromatography and phenformin as an internal standard. The modified plasma samples were analyzed by electro-spray ionization method in selective reaction monitoring mode in tandem mas...

  14. Ligand binding mode to duplex and triplex DNA assessed by combining electrospray tandem mass spectrometry and molecular modeling

    OpenAIRE

    Rosu, Frédéric; Nguyen, Chi-Hung; De Pauw, Edwin; Gabelica, Valérie

    2007-01-01

    In this paper, we report the analysis of seven benzopyridoindole and benzopyridoquinoxaline drugs binding to different duplex DNA and triple helical DNA, using an approach combining electrospray ionization mass spectrometry (ESI-MS), tandem mass spectrometry (MS/MS), and molecular modeling. The ligands were ranked according to the collision energy (CE(50)) necessary to dissociate 50% of the complex with the duplex or the triplex in tandem MS. To determine the probable ligand binding site and ...

  15. Integrated gas and liquid chromatography tandem mass spectrometry for forensic engine lubricating oil identification

    International Nuclear Information System (INIS)

    This paper presented a method for rapid chemical characterization of engine lubricating oils. Motor oils typically contain up to 5 per cent additives, such as detergent, antifoamant, dispersant, emulsifier, antioxidant, friction modifier, colour stabilizer and corrosion inhibitors. Different lube oil products usually have either different additives in various concentrations. As such, the formulation of additives in lube oil products should provide fingerprint information for forensic oil identification. The characterization method used in this study was based on a newly developed fast solvent liquid-liquid sample extraction procedure that combined the use of both liquid chromatography tandem mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS) simultaneously together with gas chromatography flame ionization detection (GC-FID). The method was used on a blind sample testing of commercially available engine lubricating products. The sample extraction procedure involved extraction of additives into acidified acetonitrile, two hexane washes of hydrophobic components of lube oil, filtration, and dilution with solvents for GC and LC analysis. The new method proved to be rapid and easy to use. It enabled the identification of unknown additives and hydrocarbons in many different types of fresh lube oils. Further tests will be needed to determine if this method can be used on real-world weathered samples. The method is part of an ongoing effort to deal with mysterious chemical spills, an important aspect of environmental protection and emergency preparedness. 8 refs., 7 figs

  16. Chemical analysis of raw and processed Fructus arctii by high-performance liquid chromatography/diode array detection-electrospray ionization-mass spectrometry

    OpenAIRE

    Kunming Qin; Qidi Liu; Hao Cai; Gang Cao; Tulin Lu; Baojia Shen; Yachun Shu; Baochang Cai

    2014-01-01

    Background: In traditional Chinese medicine (TCM), raw and processed herbs are used to treat the different diseases. Fructus Arctii, the dried fruits of Arctium lappa l. (Compositae), is widely used in the TCM. Stir-frying is the most common processing method, which might modify the chemical compositions in Fructus Arctii. Materials and Methods: To test this hypothesis, we focused on analysis and identification of the main chemical constituents in raw and processed Fructus Arctii (PFA) by hig...

  17. An isomer-specific high-energy collision-induced dissociation MS/MS database for forensic applications: a proof-of-concept on chemical warfare agent markers.

    Science.gov (United States)

    Subramaniam, Raja; Östin, Anders; Nygren, Yvonne; Juhlin, Lars; Nilsson, Calle; Åstot, Crister

    2011-09-01

    Spectra database search has become the most popular technique for the identification of unknown chemicals, minimizing the need for authentic reference chemicals. In the present study, an isomer-specific high-energy collision-induced dissociation (CID) MS/MS spectra database of 12 isomeric O-hexyl methylphosphonic acids (degradation markers of nerve agents) was created. Phosphonate anions were produced by the electrospray ionization of phosphonic acids or negative-ion chemical ionization of their fluorinated derivatives and were analysed in a hybrid magnetic-sector-time-of-flight tandem mass spectrometer. A centre-of-mass energy (E(com)) of 65 eV led to an optimal sequential carbon-carbon bond breakage, which was interpreted in terms of charge remote fragmentation. The proposed mechanism is discussed in comparison with the routinely used low-energy CID MS/MS. Even-mass (odd-electron) charge remote fragmentation ion series were diagnostic of the O-alkyl chain structure and can be used to interpret unknown spectra. Together with the odd-mass ion series, they formed highly reproducible, isomer-specific spectra that gave significantly higher database matches and probability factors (by 1.5 times) than did the EI MS spectra of the trimethylsilyl derivatives of the same isomers. In addition, ionization by negative-ion chemical ionization and electrospray ionization resulted in similar spectra, which further highlights the general potential of the high-energy CID MS/MS technique. PMID:21915956

  18. Tandem Terminal Ion Source

    International Nuclear Information System (INIS)

    OAK-B135 Tandem Terminal Ion Source. The terminal ion source (TIS) was used in several experiments during this reporting period, all for the(sup 7)Be((gamma))(sup 8)B experiment. Most of the runs used(sup 1)H(sup+) at terminal voltages from 0.3 MV to 1.5 MV. One of the runs used(sup 2)H(sup+) at terminal voltage of 1.4 MV. The other run used(sup 4)He(sup+) at a terminal voltage of 1.37 MV. The list of experiments run with the TIS to date is given in table 1 below. The tank was opened four times for unscheduled source repairs. On one occasion the tank was opened to replace the einzel lens power supply which had failed. The 10 kV unit was replaced with a 15 kV unit. The second time the tank was opened to repair the extractor supply which was damaged by a tank spark. On the next occasion the tank was opened to replace a source canal which had sputtered away. Finally, the tank was opened to replace the discharge bottle which had been coated with aluminum sputtered from the exit canal

  19. Tandem Terminal Ion Source

    International Nuclear Information System (INIS)

    OAK-B135 Tandem Terminal Ion Source. The terminal ion source (TIS) was used in several experiments during this reporting period, all for the 7Be(γ)8B experiment. Most of the runs used 1H+ at terminal voltages from 0.3 MV to 1.5 MV. One of the runs used 2H+ at terminal voltage of 1.4 MV. The other run used 4He+ at a terminal voltage of 1.37 MV. The list of experiments run with the TIS to date is given in table 1 below. The tank was opened four times for unscheduled source repairs. On one occasion the tank was opened to replace the einzel lens power supply which had failed. The 10 kV unit was replaced with a 15 kV unit. The second time the tank was opened to repair the extractor supply which was damaged by a tank spark. On the next occasion the tank was opened to replace a source canal which had sputtered away. Finally, the tank was opened to replace the discharge bottle which had been coated with aluminum sputtered from the exit canal

  20. High-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry and gas chromatography-flame ionization detection characterization of Delta5-polyenoic fatty acids in triacylglycerols from conifer seed oils.

    Science.gov (United States)

    Lísa, Miroslav; Holcapek, Michal; Rezanka, Tomás; Kabátová, Nadezda

    2007-03-30

    Edible conifer seeds can serve as a source of triacylglycerols (TGs) with unusual Delta5 unsaturated polymethylene interrupted fatty acids (UPIFAs), such as cis-5,9-octadecadienoic (taxoleic), cis-5,9,12-octadecatrienoic (pinolenic), cis-5,11-eicosadienoic (keteleeronic) and cis-5,11,14-eicosatrienoic acids (sciadonic). Conifer seed oils from European Larch (Larix decidua), Norway Spruce (Picea abies) and European Silver Fir (Abies alba) have been analyzed by non-aqueous reversed-phase high-performance liquid chromatography (NARP-HPLC) with atmospheric pressure chemical ionisation (APCI)-MS detection. The influence of different positions of double bonds in Delta5-UPIFAs on the retention and fragmentation behavior is described and used for the successful identification of TGs in each oil. TGs containing Delta5-UPIFAs have a higher retention in comparison with common TGs found in plant oils with single methylene interrupted Delta6(9)-FAs and also significantly changed relative abundances of fragment ions in APCI mass spectra. Results obtained from HPLC/MS analyses are supported by validated GC/FID analyses of fatty acid methyl esters after the transesterification. The total content of Delta5-UPIFAs is about 32% for European Larch, 27% for Norway Spruce and 20% for European Silver Fir. In total, 20 FAs with acyl chain lengths from 16 to 24 carbon atoms and from 0 to 3 double bonds have been identified in 64 triacylglycerols from 3 conifer seed oils. PMID:17307191

  1. Trace level determination of organochlorine, organophosphorus and pyrethroid pesticides in lanolin using gel permeation chromatography followed by dual gas chromatography and gas chromatography-negative chemical ionization mass spectrometric confirmation.

    Science.gov (United States)

    Jover, Eric; Bayona, Josep Maria

    2002-03-15

    A methodology for multi-class pesticide determination at trace level in lanolin is presented. Gel permeation chromatography on a Bio-Beads SX-3 column followed by a dual GC chromatographic determination has been developed. The effluent of the analytical column (50% diphenyl-methyl- or 14% cyanopropyl-phenylpolysiloxane) was split into an electron-capture and a nitrogen-phosphorus detection system. The chromatographic system was optimised for 28 pesticides commonly used to control sheep pests and corresponding to organochlorine, organophosphorus and pyretroid classes. Identification has been carried out by gas chromatography coupled to negative chemical ionization mass spectrometry. Recoveries ranged from 72 to 94% and the detection limits from 20 to 97 ng/g depending on the pesticide class, the RSDs were below 10%. Finally, the developed analytical methodology has been successfully applied to the determination of pesticides in several lanolin samples. PMID:11990995

  2. Application of Gas Chromatography-Negative Chemical Ionization Mass Spectrometry in Food Sefety Analysis%气相色谱-负化学离子源质谱法在食品安全分析中的应用

    Institute of Scientific and Technical Information of China (English)

    杨君; 王建华; 刘靖靖; 颜冬云

    2012-01-01

    气相色谱-负化学源质谱法(GC-NCI-MS)技术被广泛应用于环境、人体组织、食品等样品中污染物的定性分析和定量测定.综述了近年来气相色谱-负化学源质谱技术在食品安全分析如农药残留、兽药残留和污染物测定中的应用.%Gas chromatography-negative chemical ionization mass spectrometry (GC-NCI-MS) technology is widely used in environmental, human tissue, food and other contaminants qualitative analysis and quantitative determination. The research progress of GC-NCI-MS application in food safety analysis such as pesticide residues, veterinary drug residues and pollutants detection in recent years.

  3. Tandem Cylinder Noise Predictions

    Science.gov (United States)

    Lockhard, David P.; Khorrami, Mehdi R.; CHoudhari, Meelan M.; Hutcheson, Florence V.; Brooks, Thomas F.; Stead, Daniel J.

    2007-01-01

    In an effort to better understand landing-gear noise sources, we have been examining a simplified configuration that still maintains some of the salient features of landing-gear flow fields. In particular, tandem cylinders have been studied because they model a variety of component level interactions. The present effort is directed at the case of two identical cylinders spatially separated in the streamwise direction by 3.7 diameters. Experimental measurements from the Basic Aerodynamic Research Tunnel (BART) and Quiet Flow Facility (QFF) at NASA Langley Research Center (LaRC) have provided steady surface pressures, detailed off-surface measurements of the flow field using Particle Image Velocimetry (PIV), hot-wire measurements in the wake of the rear cylinder, unsteady surface pressure data, and the radiated noise. The experiments were conducted at a Reynolds number of 166 105 based on the cylinder diameter. A trip was used on the upstream cylinder to insure a fully turbulent shedding process and simulate the effects of a high Reynolds number flow. The parallel computational effort uses the three-dimensional Navier-Stokes solver CFL3D with a hybrid, zonal turbulence model that turns off the turbulence production term everywhere except in a narrow ring surrounding solid surfaces. The current calculations further explore the influence of the grid resolution and spanwise extent on the flow and associated radiated noise. Extensive comparisons with the experimental data are used to assess the ability of the computations to simulate the details of the flow. The results show that the pressure fluctuations on the upstream cylinder, caused by vortex shedding, are smaller than those generated on the downstream cylinder by wake interaction. Consequently, the downstream cylinder dominates the noise radiation, producing an overall directivity pattern that is similar to that of an isolated cylinder. Only calculations based on the full length of the model span were able to

  4. Structure determination of two conotoxins from Conus textile by a combination of matrix-assisted laser desorption/ionization time-of-flight and electrospray ionization mass spectrometry and biochemical methods

    DEFF Research Database (Denmark)

    Kalume, D E; Stenflo, J; Czerwiec, E;

    2000-01-01

    Two highly modified conotoxins from the mollusc Conus textile, epsilon-TxIX and Gla(1)-TxVI, were characterized by matrix-assisted laser desorption/ionization and electrospray mass spectrometry and also by electrospray ionization tandem and triple mass spectrometry in combination with enzymatic...

  5. Evaluation of the ionizing radiation effects of the 60Co on the physical, chemical and nutritional properties of Phaseolus vulgaris L. e Vigna unguiculata (L.) Walp beans

    International Nuclear Information System (INIS)

    The effects of 60 Co ionizing radiations in doses of 0; 0.5; 1.5; 2.5; 5.0 and 10 kGy on beans, Phaseolus vulgaris L., of the carioca variety and Vigna unguiculata (L.) Walp, of the macacar variety stored for 6 months were studied. The cooking time was established, and then the following analyses, and then the following analyses were carried out: Sensory, vitamins B1, B2 and B6 protein content, biological evaluation in rats [Food intake and Weight gain (in grams), apparent Digestibility (Dapp), apparent Net Protein Utilization (NPUapp) and apparent Biological Value (BVapp), as well as the applicability of detection methods of irradiated foodstuffs through germination tests, the analysis of DNA migration, thermoluminescence and analysis of the carbohydrates formed by radiation. Changes in the cooking time were observed for all doses. In doses up to 1 kGy, the nutritional quality of the irradiated beans were not altered. The application of the proposed detection methods of the irradiated foodstuffs allowed the detection of irradiated beans with doses as low as 0.5 kGy. (author)

  6. Introduction to tandem mirror physics

    International Nuclear Information System (INIS)

    This monograph, prepared jointly by the MIT Plasma Fusion Center Mirror Fusion group and SAI, Boulder, Colorado, presents a review of the development of mirror fusion theory from its conception some thirty years ago to the present. Pertinent historic experiments and their contribution are discussed to set the stage for a detailed analysis of current experiments and the problems which remain to be solved in bringing tandem mirror magnetic confinement fusion to fruition. In particular, Chapter III discusses in detail the equilibrium and stability questions which must be dealt with before tandem mirror reactors become feasible, while Chapters IV and V discuss some of the current machines and those under construction which will help to resolve critical issues in both physics and engineering whose solutions are necessary to the commercialization of tandem mirror fusion

  7. Health effects of ionizing radiation

    International Nuclear Information System (INIS)

    Ionizing radiation is energy that travels through space as electromagnetic waves or a stream of fast moving particles. In the workplace, the sources of ionizing radiation are radioactive substances, nuclear power plants, x-ray machines and nuclear devices used in medicine, research and industry. Commonly encountered types of radiation are alpha particles, beta particles and gamma rays. Alpha particles have very little penetrating power and pose a risk only when the radioactive substance is deposited inside the body. Beta particles are more penetrating than alpha particles and can penetrate the outer body tissues causing damage to the skin and the eyes. Gamma rays are highly penetrating and can cause radiation damage to the whole body. The probability of radiation-induced disease depends on the accumulated amount of radiation dose. The main health effects of ionizing radiation are cancers in exposed persons and genetic disorders in the children, grandchildren and subsequent generations of the exposed parents. The fetus is highly sensitive to radiation-induced abnormalities. At high doses, radiation can cause cataracts in the eyes. There is no firm evidence that ionizing radiation causes premature aging. Radiation-induced sterility is highly unlikely for occupational doses. The data on the combined effect of ionizing radiation and other cancer-causing physical and chemical agents are inconclusive

  8. Electrospray Ionization Mass Spectra of Dipeptide Derivatives

    Institute of Scientific and Technical Information of China (English)

    LUO, Zaigang; ZENG, Chengchu; YANG, Daoshan; HUANG, Yali; WANG, Fang; DU, Hongguang; HU, Liming

    2009-01-01

    Based on the structure of the HIV integrase core domain, dipeptide derivatives, as a type of HIV integrase in- hibitor, were synthesized, and their fragmentation pathways were investigated by electrospray ionization mass spec- trometry (ESI-MSN) in conjunction with tandem mass spectrometry (MS/MS). In order to better understand the fragmentation pathways, the MS2 and MS3 spectra of the title compound were obtained. The main fragmentation pathways occur by the cleavage of the C-CO bonds between N-(benzothiazol-2-yl)aminocarbonyl and methylene, NH-CO bonds between the NH groups and carbonyl groups. Electrospray ionization was proven to be a good method for the structural characterization and identification of this kind of compound.

  9. Study of physical, chemical and structural effects caused by ionizing radiation and preservation on human costal cartilage; Estudo dos efeitos fisicos, quimicos e estruturais ocasionados pela radiacao ionizante e preservacao em cartilagem costal humana

    Energy Technology Data Exchange (ETDEWEB)

    Martinho Junior, Antonio Carlos

    2008-07-01

    Tissue Banks around the world have stored human cartilages obtained from cadaver donors for use in several kinds of reconstructive surgeries. To ensure that such tissues are not contaminated, they have been sterilized with ionizing radiation. However, high doses of gamma radiation may cause undesirable changes in the tissues, decreasing the mechanical properties of the grafts. In this work, we evaluate physical/chemical and structural changes in deep-frozen (-70 deg C) or high concentration of glycerol (> 98%) preserved costal cartilage, before and after sterilization by ionizing radiation at 3 different doses (15, 25 and 50 kGy). Samples of human costal cartilage were obtained from 20 cadaver donors ranging between 18 and 55 years old. A {sup 60}Co irradiator was used as irradiation source. Thermogravimetry (TG), Optical Coherence Tomography (OCT) and mechanical tension and compression tests were carried out to evaluate the changes in the cartilage. Regarding the thermogravimetric results, the obtained data has shown that the TG curves have the same pattern independently of the sample irradiated or not. On the other hand, non-irradiated samples showed great variability of thermogravimetric curves among different donors and for the same donor. Concerning the mechanical tests, when cartilages were irradiated with 15 kGy, their mechanical strength to tension was increased about 24%, in both deep-froze and preserved in glycerol samples. Samples deep-frozen, when irradiated with 25 and 50 kGy, presented a decrease of their mechanical behavior smaller than those preserved in high concentrations of glycerol and irradiated with the same dose. Therefore, deep-frozen cartilages can be sterilized with doses until 50 kGy and cartilages preserved in high concentrations of glycerol can be sterilized with doses until 25 kGy without significant changes in their bio-mechanical properties.(author)

  10. Study of chemical interaction induced by ionizing radiation poly(dimethylsiloxane-g-ethylene oxide) in the poly(n-vinyl-2-pyrrolidone) and agar membrane

    International Nuclear Information System (INIS)

    Membrane composed by poly(N-vinyl-2-pyrrolidone) (PVP) and agar was formulated with and without poly(dimethylsiloxane-g-ethylene oxide) (SEO) irradiated with electron beam with doses between 10-50 kGy. The radiolytic behaviour of each component, PVP, agar and SEO, was studied when irradiated by gamma ray, in the absence and presence of air and water, by electron paramagnetic resonance (EPR) at 77 K. The chemical interaction of SEO with PVP/agar membrane was investigated by: infrared spectroscopy, energy dispersive X-ray fluorescence, dynamic-mechanical analysis, scanning electron microscopy, gel and swelling analysis. The cytotoxicity of the PVP/agar/SEO membrane was evaluated by cellular suppression. The membrane radicals from PVP (φNC.) and from water (H., OH. and H2O) was observed by EPR at 77K. The agar radicals formed by hydrogen abstraction of C1 and C3 of β-D-galactose and/or C1 and C4 of α-L-galactose, reacted primarily with water radicals in despite of they also took part in the membrane by chemical bond. The radicals from SEO (.CH2∼, .Si∼, .O∼) participated in the inter and intramolecular crosslinking as co-crosslinker by polymeric bridge. The co-crosslinked action depended on its concentration associated to PVP concentration. The presence op acrylates increases the tensile break of the PVP/agar/SEO membrane significantly. (author)

  11. Analysis of secondary organic aerosol using a Micro-Orifice Volatilization Impactor (MOVI) coupled to an ion trap mass spectrometer with atmospheric pressure chemical ionization (APCI-IT/MS)

    Science.gov (United States)

    Brueggemann, M.; Vogel, A.; Hoffmann, T.

    2012-04-01

    We describe the development and characterization of a Micro-Orifice Volatilization Impactor (MOVI) which is coupled to an ion trap mass spectrometer with atmospheric pressure chemical ionization (APCI-IT/MS), and its application in laboratory and field measurements. The MOVI-APCI-IT/MS allows the quantification of organic acids and other oxidation products of volatile organic compounds (VOCs) in secondary organic aerosols (SOA) on a semi-continuous basis. Furthermore, the vapor pressure and saturation concentration of the particle components can be estimated. The MOVI was first described in 2010 by Yatavelli and Thornton (Yatavelli and Thornton, 2010). It is a single stage, multi-nozzle impactor with 100 nozzles, each having a diameter of 150 μm. At a flow-rate of 10 L·min-1 air is drawn through the MOVI and particles are collected on a deposition plate. The cut-point diameter (d50, diameter of 50% collection efficiency) is at 130 nm. A low pressure-drop of only 5.3% of atmospheric pressure behind the nozzles allows collecting not only low-volatile but even semi-volatile compounds, which are an important part of SOA. After collecting particles hydrocarbon-free synthetic air is led over the collection surface into the APCI-IT/MS and the collection surface is heated up to 120 ° C in less than 200 s, volatilizing the sampled SOA. The vaporized compounds are transferred into the ion source and subsequently analyzed by mass spectrometry. Due to the soft ionization at atmospheric pressure the obtained mass spectra show only low fragmentations and can easily be interpreted. In laboratory experiments the MOVI-APCI-IT/MS was used for the chemical analysis of SOA generated from α-pinene-ozonolysis in a smog chamber. The limit of detection was found at 7.3 ng for pinic acid. The vapor pressure log p0 and the saturation concentration C25* for pinic acid were calculated from the desorption temperature using the method presented by Faulhaber et al. (Faulhaber et al., 2009

  12. JAERI Tandem neutron TOF spectrometer

    International Nuclear Information System (INIS)

    The layout of the neutron TOF spectrometer at JAERI Tandem Accelerator for the scattering measurement in 10-40 MeV and the data acquisition/process system are described. The result of the 28Si(n,n) and (n,n') at En=13 MeV is shown and the great improvement of the counting efficiency is obtained. (author)

  13. JAERI tandem annual report, 1982

    International Nuclear Information System (INIS)

    This annual report describes research activities which have been performed with JAERI tandem accelerator from September 1, 1981 to March 31, 1983. Summary reports of 38 papers, publications, personnel and a list of co-operative researches with universities are contained. (author)

  14. JAERI Tandem annual report 1983

    International Nuclear Information System (INIS)

    This annual report describes research activities which have been performed with JAERI tandem accelerator from April 1, 1983 to March 31, 1984. Summary reports of 32 papers, publications, personnel and a list of co-operative reserches with universities are contained. (author)

  15. Amine synthesis using tandem aza-witting/imine reduction reactions

    OpenAIRE

    Meng, Qi; 孟琪

    2013-01-01

    Nowadays, both secondary and tertiary amines are playing vital roles in modern chemical industry as well as pharmaceutical industry. Various synthetic methods of amines have also been reported due to their promising applications. In this thesis, a simple and widely applicable one-pot aza-Wittig/reduction method is reported for synthesizing both secondary and tertiary amines. Firstly, we focused on tandem aza-Wittig/reduction reactions for synthesizing secondary amines. We noticed that an a...

  16. Effect of bottom cell properties on micromorph tandem device performance

    OpenAIRE

    Delli Veneri, Paola; Mercaldo, Lucia Vittoria; PRIVATO Carlo

    2009-01-01

    Abstract Micromorph tandem solar cells represent an elegant way of overcoming the efficiency limits of single-junction solar cells and reducing the light-induced degradation of amorphous silicon films. Micromorph devices have been realized on Asahi U-type TCO-covered glass substrates by very high frequency plasma enhanced chemical vapour deposition (VHF-PECVD) at 100 MHz at low substrate temperature (150 ?C). For the bottom cell different growth regimes have been explored by changi...

  17. A high-resolution time-of-flight chemical ionization mass spectrometer utilizing hydronium ions (H3O+ ToF-CIMS) for measurements of volatile organic compounds in the atmosphere

    Science.gov (United States)

    Yuan, Bin; Koss, Abigail; Warneke, Carsten; Gilman, Jessica B.; Lerner, Brian M.; Stark, Harald; de Gouw, Joost A.

    2016-07-01

    Proton transfer reactions between hydronium ions (H3O+) and volatile organic compounds (VOCs) provide a fast and highly sensitive technique for VOC measurements, leading to extensive use of proton-transfer-reaction mass spectrometry (PTR-MS) in atmospheric research. Based on the same ionization approach, we describe the development of a high-resolution time-of-flight chemical ionization mass spectrometer (ToF-CIMS) utilizing H3O+ as the reagent ion. The new H3O+ ToF-CIMS has sensitivities of 100-1000 cps ppb-1 (ion counts per second per part-per-billion mixing ratio of VOC) and detection limits of 20-600 ppt at 3σ for a 1 s integration time for simultaneous measurements of many VOC species of atmospheric relevance. The ToF analyzer with mass resolution (m/Δm) of up to 6000 allows the separation of isobaric masses, as shown in previous studies using similar ToF-MS. While radio frequency (RF)-only quadrupole ion guides provide better overall ion transmission than ion lens system, low-mass cutoff of RF-only quadrupole causes H3O+ ions to be transmitted less efficiently than heavier masses, which leads to unusual humidity dependence of reagent ions and difficulty obtaining a humidity-independent parameter for normalization. The humidity dependence of the instrument was characterized for various VOC species and the behaviors for different species can be explained by compound-specific properties that affect the ion chemistry (e.g., proton affinity and dipole moment). The new H3O+ ToF-CIMS was successfully deployed on the NOAA WP-3D research aircraft for the SONGNEX campaign in spring of 2015. The measured mixing ratios of several aromatics from the H3O+ ToF-CIMS agreed within ±10 % with independent gas chromatography measurements from whole air samples. Initial results from the SONGNEX measurements demonstrate that the H3O+ ToF-CIMS data set will be valuable for the identification and characterization of emissions from various sources, investigation of secondary

  18. Development of a new corona discharge based ion source for high resolution time-of-flight chemical ionization mass spectrometer to measure gaseous H2SO4 and aerosol sulfate

    Science.gov (United States)

    Zheng, Jun; Yang, Dongsen; Ma, Yan; Chen, Mindong; Cheng, Jin; Li, Shizheng; Wang, Ming

    2015-10-01

    A new corona discharge (CD) based ion source was developed for a commercial high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS) (Aerodyne Research Inc.) to measure both gaseous sulfuric acid (H2SO4) and aerosol sulfate after thermal desorption. Nitrate core ions (NO3-) were used as reagent ions and were generated by a negative discharge in zero air followed by addition of excess nitrogen dioxide (NO2) to convert primary ions and hydroxyl radicals (OH) into NO3- ions and nitric acid (HNO3). The CD-HRToF-CIMS showed no detectable interference from hundreds parts per billion by volume (ppbv) of sulfur dioxide (SO2). Unlike the atmospheric pressure ionization (API) ToF-CIMS, the CD ion source was integrated onto the ion-molecule reaction (IMR) chamber and which made it possible to measure aerosol sulfate by coupling to a filter inlet for gases and aerosols (FIGAERO). Moreover, compared with a quadrupole-based mass spectrometer, the desired HSO4- signal was detected by its exact mass of m/z 96.960, which was well resolved from the potential interferences of HCO3-ṡ(H2O)2 (m/z 97.014) and O-ṡH2OṡHNO3 (m/z 97.002). In this work, using laboratory-generated standards the CD-HRToF-CIMS was demonstrated to be able to detect as low as 3.1 × 105 molecules cm-3 gaseous H2SO4 and 0.5 μg m-3 ammonium sulfate based on 10-s integration time and two times of the baseline noise. The CD ion source had the advantages of low cost and a simple but robust structure. Since the system was non-radioactive and did not require corrosive HNO3 gas, it can be readily field deployed. The CD-HRToF-CIMS can be a powerful tool for both field and laboratory studies of aerosol formation mechanism and the chemical processes that were critical to understand the evolution of aerosols in the atmosphere.

  19. An Undergraduate Experiment for the Measurement of Perfluorinated Surfactants in Fish Liver by Liquid Chromatography-Tandem Mass Spectrometry

    Science.gov (United States)

    Stock, Naomi L.; Martin, Jonathan W.; Ye, Yun; Mabury, Scott A.

    2007-01-01

    A laboratory experiment that provides students a hands-on introduction to the specific techniques of liquid chromatography-tandem mass spectrometry (LC-MS/MS) and electrospray ionization is presented. The students can thus practice the analytical principles of sample extraction, detection, quantification, and quality control using a fresh fish…

  20. Lymphoblastoid lines and skin fibroblasts from patients with tuberous sclerosis are abnormally sensitive to ionizing radiation and to a radiomimetic chemical

    International Nuclear Information System (INIS)

    Lymphoblastoid lines, derived by transforming peripheral blood lymphocytes with Epstein-Barr virus, and skin fibroblast lines were established from two patients with tuberous sclerosis. The number of viable lymphoblastoid cells was determined by their ability to exclude the vital dye trypan blue after their irradiation with x-rays or 254 nm ultraviolet light. The growth of fibroblasts was determined by their ability to form colonies after treatment with the radiomimetic, DNA-damaging chemical N-methyl-N'-nitro-N-nitrosoguanidine. The tuberous sclerosis lymphoblastoid lines were hypersensitive to x-rays but had normal sensitivity to the ultraviolet radiation. The tuberous sclerosis fibroblast lines were hypersensitive to the N-methyl-N'-nitro-N-nitrosoguanidine. The hypersensitivity of tuberous sclerosis cells to x-rays and to N-methyl-N'-nitro-N-nitrosoguanidine is believed to reflect defective repair of DNA damaged by these agents and may provide the basis for in vitro, including prenatal, diagnostic tests for tuberous sclerosis

  1. Detection of explosives on skin using ambient ionization mass spectrometry.

    Science.gov (United States)

    Justes, Dina R; Talaty, Nari; Cotte-Rodriguez, Ismael; Cooks, R Graham

    2007-06-01

    Single nanogram amounts of the explosives TNT, RDX, HMX, PETN and their mixtures were detected and identified in a few seconds on the surface of human skin without any sample preparation by desorption electrospray ionization (DESI) using a spray solution of methanol-water doped with sodium chloride to form the chloride adducts with RDX, HMX, and PETN while TNT was examined as the radical anion and tandem mass spectrometry was used to confirm the identifications. PMID:17520116

  2. Dynamic Biodistribution of Icaritin and Its Phase-II Metabolite in Rat Tissues by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry.

    Science.gov (United States)

    Zhang, Shuang-Qing

    2016-01-01

    Icaritin (ICT), a major component in herb Epimedium brevicornum Maxim., shows beneficial effects for the treatment of osteoporosis and various cancers, and is predominantly metabolized to glucuronidated icaritin (GICT). Although clinical trials of ICT have exhibited good safety and tolerance, the dynamic bioditributions of ICT and GICT have not been reported. In the present study, the chemical structure of GICT was firstly reported, and a reliable ultra-high performance liquid chromatography-tandem mass spectrometry method (UHPLC-MS/MS) was firstly established for the simultaneous quantifications of ICT and GICT in rat tissues. The dynamic distribution of ICT and GICT in rat tissues and their pharmacokinetic parameters have been reported for the first time. ICT, GICT and the internal standard coumestrol were separated on a C18 column with a gradient mobile phase of acetonitrile and water containing ammonium formate and formic acid at a flow rate of 0.3 mL min(-1). The analytes were quantified by a triple quadrupole tandem mass spectrometer in the negative ionization mode. The lower limit of quantification values for ICT and GICT were 0.2 and 2 ng mL(-1), respectively. Good selectivity, linearity, accuracy, precision and recovery were achieved, and no significant matrix effect was observed. The UHPLC-MS/MS was firstly applied to a dynamic biodistribution study of ICT and GICT in rats, following an intraperitoneal administration of ICT at a dose of 10 mg kg(-1). PMID:27302583

  3. Ionization Energies of Lanthanides

    Science.gov (United States)

    Lang, Peter F.; Smith, Barry C.

    2010-01-01

    This article describes how data are used to analyze the pattern of ionization energies of the lanthanide elements. Different observed pathways of ionization between different ground states are discussed, and the effects of pairing, exchange, and orbital interactions on ionization energies of the lanthanides are evaluated. When all the above…

  4. Foodstuffs preservation by ionization

    International Nuclear Information System (INIS)

    This document contains all the papers presented at the meeting on foodstuffs preservation by ionization. These papers deal especially with the food ionization process, its development and the view of the food industry on ionization. Refs and figs (F.M.)

  5. Ionization in liquids

    International Nuclear Information System (INIS)

    During the 1987--1990 reporting period, studies were conducted that entailed the direct measurement of the transport and reaction properties of excess electrons in nonpolar liquids through the use of pulse-conductivity techniques. The results obtained from these studies should be applicable toward the development of a better understanding of the primary ionizing event in liquids as well as to providing physico-chemical information that is pertinent to electron-transfer processes that are ubiquitous in biological systems. Progress was also made in developing a better understanding of electron attachment reactions in liquids through measurements of the electron attachment rate constants, kes, of a variety of electron-attaching solutes. The effects of several functional groups substituted at different positions on benzene were studied in liquid cyclohexane and isooctane. The electron-attaching properties of chemicals having well characterized carcinogenic properties were studied in cyclohexane to determine if the measure of electron-accepting potential that ke provides can elucidate the role that electrons play in the initiation step of carcinogenesis. The kes that were measured indicate that the ke-carcinogenicity correlation that was observed can be used to complement short-term carcinogen-screening bioassays to identify potential carcinogens. 115 refs., 6 tabs

  6. Matrix isolation studies of the interactions of BF3 with water and substituted diethyl ethers. Chemical ionization mass spectrometric determination of the proton affinity of (CF3CH2)2O

    Science.gov (United States)

    Ball, David W.; Zehe, Michael J.

    1993-01-01

    BF3 was co-condensed with H2O, D2O, (C2H5)2O, (CF3CH2)2O, and (C2F5)2O in excess argon at 15 K. Infrared spectra of BF3/water isolated in solid argon provided a more complete analysis of the BF3--H2O complex than previously published. Infrared spectra of the matrices showed a definite Lewis acid-base interaction between BF3 and diethyl ether; a weak but definite interaction with bis (2,2,2-trifluorodiethyl) ether, and no observable interaction with perfluorodiethyl ether. Thus, the ether data indicate a clear trend between strength of interaction with BF3 and the degree of F substitution. To support and explain the emerging relationship between interaction strength and the basicity of the oxygen-containing molecule, the proton affinity of (CF3CH2)2O was measured using chemical ionization mass spectrometry. The implications of the results for lubricant/metal oxide surface interactions are discussed.

  7. Quality classification of Spanish olive oils by untargeted gas chromatography coupled to hybrid quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization and metabolomics-based statistical approach.

    Science.gov (United States)

    Sales, C; Cervera, M I; Gil, R; Portolés, T; Pitarch, E; Beltran, J

    2017-02-01

    The novel atmospheric pressure chemical ionization (APCI) source has been used in combination with gas chromatography (GC) coupled to hybrid quadrupole time-of-flight (QTOF) mass spectrometry (MS) for determination of volatile components of olive oil, enhancing its potential for classification of olive oil samples according to their quality using a metabolomics-based approach. The full-spectrum acquisition has allowed the detection of volatile organic compounds (VOCs) in olive oil samples, including Extra Virgin, Virgin and Lampante qualities. A dynamic headspace extraction with cartridge solvent elution was applied. The metabolomics strategy consisted of three different steps: a full mass spectral alignment of GC-MS data using MzMine 2.0, a multivariate analysis using Ez-Info and the creation of the statistical model with combinations of responses for molecular fragments. The model was finally validated using blind samples, obtaining an accuracy in oil classification of 70%, taking the official established method, "PANEL TEST", as reference. PMID:27596432

  8. A switchable reagent ion high resolution time-of-flight chemical ionization mass spectrometer for real-time measurement of gas phase oxidized species: characterization from the 2013 Southern Oxidant and Aerosol Study

    Directory of Open Access Journals (Sweden)

    P. Brophy

    2015-03-01

    Full Text Available A novel configuration of the Aerodyne high resolution time-of-flight chemical ionization mass spectrometer (HR-TOF-CIMS as a switchable reagent ion (SRI HR-TOF-CIMS is presented and described along with data collected at the Southern Oxidant and Aerosol Study (SOAS during the summer of 2013. The calibration system and reduced pressure gas-phase inlet are characterized. The average limit of detection and limit of quantification for formic acid during SOAS are 82 and 863 ppt, respectively, corresponding to an average sensitivity of 13 ± 5 Hz ppt−1. Hourly background determinations and calibrations are shown to be essential for tracking instrument performance and accurately quantifying formic acid. Maximum daytime formic acid concentrations of 10 ppb are reported during SOAS, and a strong diel cycle is observed leading to night time concentrations below the limit of quantification. Other species presented exhibit diel behavior similar to formic acid. The concept of the mass defect enhancement plot and the use of signal-to-noise are described in detail as a method for investigating HR-TOF-CIMS spectra in an effort to reduce data complexity.

  9. Quantification of salsolinol enantiomers by stable isotope dilution liquid chromatography with tandem mass spectrometric detection

    OpenAIRE

    Cai, Min; Liu, Yi-Ming

    2008-01-01

    Salsolinol, 1-methyl-6,7-dihydroxy-2,3,4,5-tetrahydroisoquinoline (SAL), is a precursor of a Parkinsonian neurotoxin, N-methysalsolinol (N-methyl-SAL). Previous studies have shown that individual enantiomers of N-methyl-SAL possess distinct neurotoxicological properties. In this work, a chiral high-performance liquid chromatography (HPLC) method with electrospray ionization tandem mass spectrometric (ESI-MS/MS) detection was developed for the quantification of (R/S)-SAL enantiomers. Enantiose...

  10. Direct Quantification of Cannabinoids and Cannabinoid Glucuronides in Whole Blood by Liquid Chromatography Tandem Mass Spectrometry

    OpenAIRE

    Schwope, David M.; Scheidweiler, Karl B.; Huestis, Marilyn A.

    2011-01-01

    The first method for quantifying cannabinoids and cannabinoid glucuronides in whole blood by liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed and validated. Solid-phase extraction followed protein precipitation with acetonitrile. HPLC separation was achieved in 16 min via gradient elution. Electrospray ionization was utilized for cannabinoid detection; both positive (Δ9-tetrahydrocannabinol [THC], cannabinol [CBN]) and negative (11-hydroxy-THC [11-OH-THC], 11-nor-9-carb...

  11. Evaluation of the ionizing radiation 60Co effect on the physical, chemical and nutritional properties of different cultivars of soybean grains (Glycine max (L.))

    International Nuclear Information System (INIS)

    With the increase of the world population, creative strategies will be necessary to control food production. To achieve this challenge, new cultivars have been development, though different techniques and characteristics. To improve food conservation, a plant of methods can be used. The use of Cobalto-60 radiation is a secure and useful method to increase the life time of foods. Due to the commercial and nutritional importance of soybean, some alterations must be studied. This study has the objective to determinate this alterations caused by irradiation (with doses of 2, 4 and 8 kGy) in raw and cooked grain of five different cultivars of soybean (BRS 212, BRS 213, BRS 214, 231 BRS and E48), this study includes analysis of time cooking and hydratation, and chemical analysis of proximate composition, in vitro digestibility of proteins, percentage of deamidation , phenolics compounds, trypsin inhibitors and tannins. The amount of water absorbed by each grain varied from 14.00 to 16.66mL, and the time cooking varied from 119.67 to 291.33 minutes. The values found for ash were 4.90 to 6.08%, for protein from 21.23 to 36.99%, for fat from 19.22 to 24.84%, soluble staple fibres from 1.37 to 4.03% and insoluble staple fibres from 15.97 to 18.87%. The deamidation percentage in the different samples varied of 17,34 to 57.79% and the digestibility in vitro from 84.45 to 89.11%. Inside of the anti nutritional factors, the total compounds phenolics varied from 3.9 to 9.7 mg/g, the units of trypsin inhibited from 24.75 to 57.53 UTI/g and the tannins from 0.02 to 0.32 mg/g. For the physical analyses it showed differences in the time of hydratation among them and the irradiation promoted reduction in the time, but not in the amount of absorbed water; in the cooking time it had reduction with the increase of the doses of radiation; the differences found in the proximate composition did not have influence with the irradiation, but with the different cultivars; for the digestibility

  12. Nanocrystal assembly for tandem catalysis

    Science.gov (United States)

    Yang, Peidong; Somorjai, Gabor; Yamada, Yusuke; Tsung, Chia-Kuang; Huang, Wenyu

    2014-10-14

    The present invention provides a nanocrystal tandem catalyst comprising at least two metal-metal oxide interfaces for the catalysis of sequential reactions. One embodiment utilizes a nanocrystal bilayer structure formed by assembling sub-10 nm platinum and cerium oxide nanocube monolayers on a silica substrate. The two distinct metal-metal oxide interfaces, CeO.sub.2--Pt and Pt--SiO.sub.2, can be used to catalyze two distinct sequential reactions. The CeO.sub.2--Pt interface catalyzed methanol decomposition to produce CO and H.sub.2, which were then subsequently used for ethylene hydroformylation catalyzed by the nearby Pt--SiO.sub.2 interface. Consequently, propanal was selectively produced on this nanocrystal bilayer tandem catalyst.

  13. "Nanocrystal bilayer for tandem catalysis"

    Energy Technology Data Exchange (ETDEWEB)

    Yamada, Yusuke; Tsung, Chia Kuang; Huang, Wenyu; Huo, Ziyang; E.Habas, Susan E; Soejima, Tetsuro; Aliaga, Cesar E; Samorjai, Gabor A; Yang, Peidong

    2011-01-24

    Supported catalysts are widely used in industry and can be optimized by tuning the composition and interface of the metal nanoparticles and oxide supports. Rational design of metal-metal oxide interfaces in nanostructured catalysts is critical to achieve better reaction activities and selectivities. We introduce here a new class of nanocrystal tandem catalysts that have multiple metal-metal oxide interfaces for the catalysis of sequential reactions. We utilized a nanocrystal bilayer structure formed by assembling platinum and cerium oxide nanocube monolayers of less than 10 nm on a silica substrate. The two distinct metal-metal oxide interfaces, CeO2-Pt and Pt-SiO2, can be used to catalyse two distinct sequential reactions. The CeO2-Pt interface catalysed methanol decomposition to produce CO and H2, which were subsequently used for ethylene hydroformylation catalysed by the nearby Pt-SiO2 interface. Consequently, propanal was produced selectively from methanol and ethylene on the nanocrystal bilayer tandem catalyst. This new concept of nanocrystal tandem catalysis represents a powerful approach towards designing high-performance, multifunctional nanostructured catalysts

  14. Physics of Partially Ionized Plasmas

    Science.gov (United States)

    Krishan, Vinod

    2016-05-01

    Figures; Preface; 1. Partially ionized plasmas here and everywhere; 2. Multifluid description of partially ionized plasmas; 3. Equilibrium of partially ionized plasmas; 4. Waves in partially ionized plasmas; 5. Advanced topics in partially ionized plasmas; 6. Research problems in partially ionized plasmas; Supplementary matter; Index.

  15. Development of chemical dosimeters

    International Nuclear Information System (INIS)

    A chemical dosimeter is a system that measures the energy by virtue of chemical changes from ionizing absorbed radiation produced unit when it is exposed to ionizing radiation. In all chemical dosimeters radiation induced chemical reaction produces at least one, initially absent species, which is properties long lived enough to determine its quantity or the change in the initial systems. Different types of chemical dosimeters were discussed such as aqueous, gaseous and solid, but the great consideration was given to aqueous systems because of their vital role in setting many processes.(Author)

  16. The characterization of tandem and corrugated wings

    Science.gov (United States)

    Lian, Yongsheng; Broering, Timothy; Hord, Kyle; Prater, Russell

    2014-02-01

    Dragonfly wings have two distinct features: a tandem configuration and wing corrugation. Both features have been extensively studied with the aim to understand the superior flight performance of dragonflies. In this paper we review recent development of tandem and corrugated wing aerodynamics. With regards to the tandem configuration, this review will focus on wing/wing and wing/vortex interactions at different flapping modes and wing spacing. In addition, the aerodynamics of tandem wings under gusty conditions will be reviewed and compared with isolated wings to demonstrate the gust resistance characteristics of flapping wings. Regarding corrugated wings, we review their structural and aerodynamic characteristics.

  17. Ionization applications in food industry - Generalities

    International Nuclear Information System (INIS)

    This paper outlines different applications of the ionization in food treatments and their purposes. Irradiation of food with low doses (below 1 kgy) is used for germination inhibition, insects sterilization, disinfestation and senescence delays. Applications with medium doses (from 1 to 10 kgy) are used for extension of shelf life, elimination of pathogenic microorganisms and improving technological properties. Applications with high doses (superior to 10 Kgy) are used for food sterilization, only in some specific cases. Necessary doses in various applications of food ionization are given as well as minimal doses for food sterilization. In some cases where treatment of food by only ionization do not permit to attain the fixed object, ionizing treatment is combined with an other type of treatment as: refrigeration, heat treatments, packing, dehydration and chemical treatments. 3 tabs., 5 refs. (F.M.)

  18. Sensitive determination of trace urinary 3-hydroxybenzo[a]pyrene using ionic liquids-based dispersive liquid-liquid microextraction followed by chemical derivatization and high performance liquid chromatography-high resolution tandem mass spectrometry.

    Science.gov (United States)

    Hu, Huan; Liu, Baizhan; Yang, Jun; Lin, Zuomin; Gan, Wuer

    2016-08-01

    3-Hydroxybenzo[a]pyrene (3-OHBaP) is widely used as a biomarker for assessing carcinogenic benzo[a]pyrene exposure risks. However, monitoring urinary 3-OHBaP suffers from an insufficient sensitivity due to the pg/mL level in urine excretion. In this study, a sensitive method for determination trace urinary 3-OHBaP was developed, involving enzymatic hydrolysis of the glucuronide and sulfate conjugates, ionic liquids dispersive liquid-liquid microextraction (IL-DLLME) enrichment, derivatization with dansyl chloride and HPLC-HRMS/MS analysis in the positive ion mode. Using IL-DLLME makes the enrichment of trace 3-OHBaP very simple, time-saving, efficiency and environmentally-friendly. To enhanced HPLC-HRMS/MS response, an MS-friendly dansyl group was introduced to increase the ionization and fragmentation efficiency. The optimal IL-DLLME extraction parameters and derivatization reaction conditions were investigated. Good linearity was obtained over a concentration range of 0.6-50.0pg/mL with correlation coefficients (r(2)) of 0.9918. The limit of detection (LOD) and limit of quantification (LOQ) values were 0.2pg/mL and 0.58pg/mL, respectively. The recoveries were 92.0±4.2% with the intra-day and inter-day RSD values ranged from 2.2% to 3.8% and from 3.3% to 6.8%, respectively. The proposed IL-DLLME-Dansylation-HPLC-HRMS/MS method was successfully applied to determine urinary 3-OHBaP of non-occupational exposed smokers and nonsmokers. PMID:27294533

  19. ESTIMATION OF IONIZATION CONSTANTS OF AZO DYES AND RELATED AROMATIC AMINES: ENVIRONMENTAL IMPLICATIONS

    Science.gov (United States)

    Ionization constants for 214 dye molecules were calculated from molecular structures using the chemical reactivity models developed in SPARC (SPARC Performs Automated Reasoning in Chemistry). hese models used fundamental chemical structure theory to predict chemical reactivities ...

  20. Ultrasound-assisted dispersive liquid-liquid microextraction combined with gas chromatography-mass spectrometry in negative chemical ionization mode for the determination of polybrominated diphenyl ethers in water.

    Science.gov (United States)

    Zhang, Qian; Liang, Tao; Guan, Lili

    2013-04-01

    A simple and economical method for the determination of eight polybrominated diphenyl ethers (BDE-28, 47, 99, 100,153,154,183, and 209) in water was developed. This method involves the use of ultrasound-assisted dispersive liquid-liquid microextraction combined with GC-MS in negative chemical ionization mode. Various parameters affecting the extraction efficiency, including the type and volume of extraction and dispersive solvents, salt concentration, extraction time, and ultrasonic time, were investigated. A volume of 1.0 mL of acetone (dispersive solvent) containing 10 μL tetrachloroethylene (extraction solvent) was injected into 5.0 mL of water samples and then emulsified by ultrasound for 2.0 min to produce the cloudy solution. Under the optimal condition, the enrichment factors for the eight PBDEs were varied from 845- to 1050-folds. Good linearity was observed in the range of 1.0-200 ng L(-1) for BDE-28, 47, 99, and 100; 5.0-200 ng L(-1) for BDE-153, 154, and 183; and 5.0-500 ng L(-1) for BDE-209. The RSD values were in the range of 2.5-8.4% (n = 5) and the LODs ranged from 0.40 to 2.15 ng L(-1) (S/N = 3). The developed method was applied for the determination of eight BPDEs in the river and lake water samples, and the mean recoveries at spiking levels of 5.0 and 50.0 ng L(-1) were in the range of 70.6-105.1%. PMID:23483741

  1. Part-per-trillion level determination of antifouling pesticides and their byproducts in seawater samples by off-line solid-phase extraction followed by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    Science.gov (United States)

    Martínez, K; Ferrer, I; Barceló, D

    2000-05-19

    A new method for the simultaneous determination of antifouling pesticides and some of their byproducts such as dichlofluanid, diuron and its byproducts [demethyldiuron and 1-(3,4-dichlorophenyl)urea], (2-thiocyanomethylthio)ben: zothiazole, chlorothalonil, Sea-nine 211, Irgarol 1051 and one of its byproducts (2-methylthio-4-tert.-butylamino-s-triazine) in seawater was developed. The extraction of these compounds from the filtered seawater samples was performed off-line with different solid-phase extraction sorbents using (I) a 500 mg graphitized carbon black cartridge (ENVI-Carb) and (II) 200 mg polymeric cartridges (LiChrolut EN and Isolute ENV+) and passing 500 ml of the sample through these cartridges. The detection was carried out by reversed-phase high-performance liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry both in the negative and positive ion modes. The recovery ranged from 76 to 96% for the whole antifouling group with the ENVI-Carb cartridges and the detection limit was at the part-per-trillion level except for TCMTB. The method utilizing the polymeric cartridge proved to be very useful, time saving and with good recoveries when only Irgarol and its byproduct, Sea-nine 211 and diuron and its byproducts, have to be analyzed. The different cartridges were applied to the analysis of these pesticides in different marinas of the Catalan coast; diuron, dichlofluanid, Sea-nine 211, Irgarol as well as demethyldiuron and the Irgarol byproduct being the must ubiquitous pollutants. Maximum concentration levels were 2-3.5 microg/l of diuron and Sea-nine 211, respectively. PMID:10870693

  2. Resonance ionization spectroscopy 1986

    International Nuclear Information System (INIS)

    The paper presents the proceedings of the Third International Symposium on Resonance Ionization Spectroscopy and its Applications, held at the University College of Swansea, Wales, 1986. The Symposium is divided into eight main sections entitled: photophysics and spectroscopy, noble gas atom counting, resonance ionization mass spectrometry, materials and surface analysis, small molecules, medical and environmental applications, resonance ionization and materials separation, and elementary particles and nuclear physics. Thirty papers were chosen for INIS and indexed separately. (U.K.)

  3. Abnormal ionization in sonoluminescence

    Institute of Scientific and Technical Information of China (English)

    张文娟; 安宇

    2015-01-01

    Sonoluminescence is a complex phenomenon, the mechanism of which remains unclear. The present study reveals that an abnormal ionization process is likely to be present in the sonoluminescing bubble. To fit the experimental data of previous studies, we assume that the ionization energies of the molecules and atoms in the bubble decrease as the gas density increases and that the decrease of the ionization energy reaches about 60%–70%as the bubble flashes, which is difficult to explain by using previous models.

  4. Ionizing Radiation and Life

    OpenAIRE

    Dartnell, L. R.

    2011-01-01

    Ionizing radiation is a ubiquitous feature of the Cosmos, from exogenous cosmic rays (CR) to the intrinsic mineral radioactivity of a habitable world, and its influences on the emergence and persistence of life are wide-ranging and profound. Much attention has already been focused on the deleterious effects of ionizing radiation on organisms and the complex molecules of life, but ionizing radiation also performs many crucial functions in the generation of habitable planetary environments and ...

  5. Analytical instruments, ionization sources, and ionization methods

    Science.gov (United States)

    Atkinson, David A.; Mottishaw, Paul

    2006-04-11

    Methods and apparatus for simultaneous vaporization and ionization of a sample in a spectrometer prior to introducing the sample into the drift tube of the analyzer are disclosed. The apparatus includes a vaporization/ionization source having an electrically conductive conduit configured to receive sample particulate which is conveyed to a discharge end of the conduit. Positioned proximate to the discharge end of the conduit is an electrically conductive reference device. The conduit and the reference device act as electrodes and have an electrical potential maintained between them sufficient to cause a corona effect, which will cause at least partial simultaneous ionization and vaporization of the sample particulate. The electrical potential can be maintained to establish a continuous corona, or can be held slightly below the breakdown potential such that arrival of particulate at the point of proximity of the electrodes disrupts the potential, causing arcing and the corona effect. The electrical potential can also be varied to cause periodic arcing between the electrodes such that particulate passing through the arc is simultaneously vaporized and ionized. The invention further includes a spectrometer containing the source. The invention is particularly useful for ion mobility spectrometers and atmospheric pressure ionization mass spectrometers.

  6. Quantifying Uranium Isotope Ratios Using Resonance Ionization Mass Spectrometry: The Influence of Laser Parameters on Relative Ionization Probability

    OpenAIRE

    Isselhardt, Brett Hallen

    2011-01-01

    Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure relative uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process to provide a distinction between uranium atoms and potential isobars without the aid of chemical purification and separation. We explore the laser parameters critical to the ionization process and their effects on the measured isotope ratio. Specifically, the use of broad bandwidth lasers with aut...

  7. Tandem mirror technology demonstration facility

    International Nuclear Information System (INIS)

    This report describes a facility for generating engineering data on the nuclear technologies needed to build an engineering test reactor (ETR). The facility, based on a tandem mirror operating in the Kelley mode, could be used to produce a high neutron flux (1.4 MW/M2) on an 8-m2 test area for testing fusion blankets. Runs of more than 100 h, with an average availability of 30%, would produce a fluence of 5 mW/yr/m2 and give the necessary experience for successful operation of an ETR

  8. Tandem mirror technology demonstration facility

    Energy Technology Data Exchange (ETDEWEB)

    1983-10-01

    This report describes a facility for generating engineering data on the nuclear technologies needed to build an engineering test reactor (ETR). The facility, based on a tandem mirror operating in the Kelley mode, could be used to produce a high neutron flux (1.4 MW/M/sup 2/) on an 8-m/sup 2/ test area for testing fusion blankets. Runs of more than 100 h, with an average availability of 30%, would produce a fluence of 5 mW/yr/m/sup 2/ and give the necessary experience for successful operation of an ETR.

  9. Non disturbing characterization and quantification of natural organic matter (NOM) contained in clay rock pore water by mass spectrometry using electro-spray and atmospheric pressure chemical ionization modes

    International Nuclear Information System (INIS)

    formation is of great importance. In this context, establishing accurate sequencing of structural units for the DOM shall be attempted. The present work is focused on small organic molecules that are present in the COx formation and that could also play a key role in the migration processes. It would be valuable to develop rapid analytical methods that require only a small sample volume and minimal pretreatment. Of particular importance is the ability to analyze bulk pore water samples as opposed to samples subjected to specific extraction techniques, fractionation, and/or concentration. Mass Spectrometry with either the Electro-Spray or the Atmospheric Pressure Chemical Ionization modes has been proved to be a powerful tool for aquatic humic substances since it allows the determination of the molecular weight distribution and the access to the different molecular weights. In this study, we have employed ESI-MS and APCI-MS to identify the chemical composition of NOM contained in the pore water from the argillite clay rock. Due to the very small quantities of COx pore water available from boreholes, these techniques are thus very suitable. The DOM in pore water has never been characterized on a well preserved pore water sample. The following aspects were considered in the present work: (1) the use of either ESI or APCI to select the most appropriated mode of ionization for providing the best information depending on the class of compound examined (2) a unique and original experimental process developed to get pore water from a core sample (3) the determination of concentration of dissolved organic matter and the evaluation of the organic matter maturity by Excitation-Emission Matrix (EEM) spectroscopy and (4) the application of the proposed instrumental methods for the characterization of organic components from natural pore waters. For the first time to our knowledge, a quite exhaustive inventory of the small organic compounds presents is given without proceeding to any

  10. IONIZATION IN ATMOSPHERES OF BROWN DWARFS AND EXTRASOLAR PLANETS. V. ALFVÉN IONIZATION

    International Nuclear Information System (INIS)

    Observations of continuous radio and sporadic X-ray emission from low-mass objects suggest they harbor localized plasmas in their atmospheric environments. For low-mass objects, the degree of thermal ionization is insufficient to qualify the ionized component as a plasma, posing the question: what ionization processes can efficiently produce the required plasma that is the source of the radiation? We propose Alfvén ionization as a mechanism for producing localized pockets of ionized gas in the atmosphere, having sufficient degrees of ionization (≥10–7) that they constitute plasmas. We outline the criteria required for Alfvén ionization and demonstrate its applicability in the atmospheres of low-mass objects such as giant gas planets, brown dwarfs, and M dwarfs with both solar and sub-solar metallicities. We find that Alfvén ionization is most efficient at mid to low atmospheric pressures where a seed plasma is easier to magnetize and the pressure gradients needed to drive the required neutral flows are the smallest. For the model atmospheres considered, our results show that degrees of ionization of 10–6-1 can be obtained as a result of Alfvén ionization. Observable consequences include continuum bremsstrahlung emission, superimposed with spectral lines from the plasma ion species (e.g., He, Mg, H2, or CO lines). Forbidden lines are also expected from the metastable population. The presence of an atmospheric plasma opens the door to a multitude of plasma and chemical processes not yet considered in current atmospheric models. The occurrence of Alfvén ionization may also be applicable to other astrophysical environments such as protoplanetary disks

  11. IONIZATION IN ATMOSPHERES OF BROWN DWARFS AND EXTRASOLAR PLANETS. V. ALFVÉN IONIZATION

    Energy Technology Data Exchange (ETDEWEB)

    Stark, C. R.; Helling, Ch.; Rimmer, P. B. [SUPA, School of Physics and Astronomy, University of St Andrews, St Andrews, KY16 9SS (United Kingdom); Diver, D. A., E-mail: craig.stark@st-andrews.ac.uk [SUPA, School of Physics and Astronomy, Kelvin Building, University of Glasgow, Glasgow, G12 8QQ (United Kingdom)

    2013-10-10

    Observations of continuous radio and sporadic X-ray emission from low-mass objects suggest they harbor localized plasmas in their atmospheric environments. For low-mass objects, the degree of thermal ionization is insufficient to qualify the ionized component as a plasma, posing the question: what ionization processes can efficiently produce the required plasma that is the source of the radiation? We propose Alfvén ionization as a mechanism for producing localized pockets of ionized gas in the atmosphere, having sufficient degrees of ionization (≥10{sup –7}) that they constitute plasmas. We outline the criteria required for Alfvén ionization and demonstrate its applicability in the atmospheres of low-mass objects such as giant gas planets, brown dwarfs, and M dwarfs with both solar and sub-solar metallicities. We find that Alfvén ionization is most efficient at mid to low atmospheric pressures where a seed plasma is easier to magnetize and the pressure gradients needed to drive the required neutral flows are the smallest. For the model atmospheres considered, our results show that degrees of ionization of 10{sup –6}-1 can be obtained as a result of Alfvén ionization. Observable consequences include continuum bremsstrahlung emission, superimposed with spectral lines from the plasma ion species (e.g., He, Mg, H{sub 2}, or CO lines). Forbidden lines are also expected from the metastable population. The presence of an atmospheric plasma opens the door to a multitude of plasma and chemical processes not yet considered in current atmospheric models. The occurrence of Alfvén ionization may also be applicable to other astrophysical environments such as protoplanetary disks.

  12. MR-Tandem: parallel X!Tandem using Hadoop MapReduce on Amazon Web Services

    OpenAIRE

    Pratt, Brian; Howbert, J. Jeffry; Tasman, Natalie I.; Nilsson, Erik J.

    2011-01-01

    Summary: MR-Tandem adapts the popular X!Tandem peptide search engine to work with Hadoop MapReduce for reliable parallel execution of large searches. MR-Tandem runs on any Hadoop cluster but offers special support for Amazon Web Services for creating inexpensive on-demand Hadoop clusters, enabling search volumes that might not otherwise be feasible with the compute resources a researcher has at hand. MR-Tandem is designed to drop in wherever X!Tandem is already in use and requires no modifica...

  13. Aliphatic and aromatic amines in atmospheric aerosol particles: comparison of three ionization techniques in liquid chromatography-mass spectrometry and method development.

    Science.gov (United States)

    Ruiz-Jiménez, José; Hautala, Sanna; Parshintsev, Jevgeni; Laitinen, Totti; Hartonen, Kari; Petäjä, Tuukka; Kulmala, Markku; Riekkola, Marja-Liisa

    2012-08-15

    A complete methodology was developed for the determination of ten aliphatic and nine aromatic amines in atmospheric aerosol particles. Before the liquid chromatography - tandem mass spectrometric separation and determination, the derivatization reaction of the analytes using dansyl chloride was accelerated by ultrasounds. From three different ionization techniques studied electrospray ionization was superior in terms of sensitivity, linearity, repeatability and reproducibility over atmospheric pressure chemical ionization and photoionization for the target analytes. The method developed was validated for the gas phase, 30 nm and total suspended atmospheric aerosol particles. The method quantification limits ranged between 1.8 and 71.7 pg. The accuracy and the potential matrix effects were evaluated using a standard addition methodology. Recoveries from 92.1% to 109.1%, the repeatability from 0.6% to 8.4% and the reproducibility from 2.3% to 9.8% were obtained. The reliability of the methodology was proved by the statistical evaluation. Finally, the developed methodology was applied to the determination of the target analytes in eight size separated ultrafine particulate (Dp=30±4 nm) samples and in eight total suspended particulate samples collected at the SMEAR II station. The mean concentrations for aliphatic amines were between 0.01 and 42.67 ng m(-3) and for aromatic amines between 0.02 and 1.70 ng m(-3). Thirteen amines were quantified for the first time in 30 nm aerosol particles. PMID:22841047

  14. Parametric studies of tandem mirror reactors

    International Nuclear Information System (INIS)

    This report, along with its companion, An Improved Tandem Mirror Reactor, discusses the recent progress and present status of our tandem mirror reactor studies. This report presents the detailed results of parametric studies up to, but not including, the very new ideas involving thermal barriers

  15. The injector of the Utrecht en tandem

    OpenAIRE

    Zwol, N.A. van; van der Borg, K.; de Haas, A.P.; Hoogenboom, A.M.; Strasters, B.A.; Vermeer, A.

    1984-01-01

    An injector has been built to obtain improved beam transmission through the EN tandem. The injector has been provided with a 90° analysing magnet, m/Δm = 300, and 130 kV preacceleration. Beam optics calculations have been made for the injector and tandem. The injector has been equipped with a fiber optics control and data acquisition system.

  16. Computational Prediction of Electron Ionization Mass Spectra to Assist in GC/MS Compound Identification.

    Science.gov (United States)

    Allen, Felicity; Pon, Allison; Greiner, Russ; Wishart, David

    2016-08-01

    We describe a tool, competitive fragmentation modeling for electron ionization (CFM-EI) that, given a chemical structure (e.g., in SMILES or InChI format), computationally predicts an electron ionization mass spectrum (EI-MS) (i.e., the type of mass spectrum commonly generated by gas chromatography mass spectrometry). The predicted spectra produced by this tool can be used for putative compound identification, complementing measured spectra in reference databases by expanding the range of compounds able to be considered when availability of measured spectra is limited. The tool extends CFM-ESI, a recently developed method for computational prediction of electrospray tandem mass spectra (ESI-MS/MS), but unlike CFM-ESI, CFM-EI can handle odd-electron ions and isotopes and incorporates an artificial neural network. Tests on EI-MS data from the NIST database demonstrate that CFM-EI is able to model fragmentation likelihoods in low-resolution EI-MS data, producing predicted spectra whose dot product scores are significantly better than full enumeration "bar-code" spectra. CFM-EI also outperformed previously reported results for MetFrag, MOLGEN-MS, and Mass Frontier on one compound identification task. It also outperformed MetFrag in a range of other compound identification tasks involving a much larger data set, containing both derivatized and nonderivatized compounds. While replicate EI-MS measurements of chemical standards are still a more accurate point of comparison, CFM-EI's predictions provide a much-needed alternative when no reference standard is available for measurement. CFM-EI is available at https://sourceforge.net/projects/cfm-id/ for download and http://cfmid.wishartlab.com as a web service. PMID:27381172

  17. Multiphoton ionization of atoms

    International Nuclear Information System (INIS)

    The paper is devoted to the analysis of high intensity effects which result from multiphoton ionization of atoms in a high laser intensity, ranging from 1010 to 1015 W cm-2. Resonant multiphoton ionization of atoms, the production of multiply charged ions, and electron energy spectra, are all discussed. (U.K.)

  18. Application of ionizing radiation

    International Nuclear Information System (INIS)

    Fundamental studies by the Nuclear Research Institute concerning the use of ionizing radiations are reported. The ROZA irradiation plant is used for sterilization in medicine and for historic objects preservation. Ionizing radiation is used in the radiation treatment of cables and drinking water. Radiopharmaceuticals are developed. The Institute is an all-state centre for research and development of semiconductor detectors. (M.S.)

  19. Radioactive beams produced by the ISOL method: development for laser ionization and for surface ionization; Faisceaux exotiques par methode ISOL: developpements pour l'ionisation par laser et l'ionisation de surface

    Energy Technology Data Exchange (ETDEWEB)

    Hosni, Faouzi

    2004-10-01

    The works were carried out in the framework of the research program PARRNe (production of radioactive neutron-rich nuclei). This program aims to determine optimal conditions to produce intense beams of neutron-rich isotopes. This thesis treats multiple technical aspects related to the production of separate radioactive isotopes in line (ISOL). It deals mainly with the development of the target-source unit which is the key element for projects such as SPIRAL-2 or EURISOL.The first part presents the various methods using fission as production mode and compares them: fission induced by thermal neutrons, induced by fast neutrons and photofission. The experiment carried out at CERN validated the interest of the photofission as a promising production mode of radioactive ions. That is why the institute of nuclear physics of Orsay decided to build a linear electron accelerator at the Tandem d'Orsay (ALTO).The second part of this thesis deals with the development of uranium targets. The X-rays diffraction and Scanning Electron Microscopy have been used as analysis techniques. They allowed to determine the chemical and structural characteristics of uranium carbide targets as function of various heating temperatures. After the production, the process of ionization has been studied. Two types of ion source have been worked out: the first one is a surface ion source and the second one is a source based on resonant ionization by laser. These two types of sources will be used for the ALTO project. (author)

  20. Multiphoton ionization of atoms

    International Nuclear Information System (INIS)

    This article provides an overview of the current understanding of multiphoton ionization of atoms. It begins with an introductory section to explain the background of the subject. Then the article develops the three topics which have been central themes of discussion in multiphoton ionization of atoms these past few years: multiply charged ion production, very high order harmonic generation, and above-threshold ionization, a name given to the absorption of a very large number of photons by an already ionized electron. A large part of the review is devoted to some theoretical aspects of multiphoton ionization of atoms and especially non-perturbative theories. Finally the article considers the very near future prospects of laser-electron interactions and more generally laser-matter interactions at 1018 -1019 W cm-2, an intensity range now within reach due to new short pulse laser technology. (author)